Binders containing an aldehyde-based resin and an isocyanate-based resin and methods for making composite lignocellulose products therefrom

ABSTRACT

Binders, methods for making same, and methods for making composite lignocellulose products therefrom. The binder can include about 30 wt % to about 40 wt % of solids that include a urea-modified aldehyde-based resin; about 0.1 wt % to about 3 wt % of solids that include an isocyanate-based resin; about 0.1 wt % to about 12 wt % of an extender; and about 50 wt % to about 62 wt % of water, where all weight percent values are based on a total weight of the binder. The binder can have a sodium hydroxide equivalent weight alkalinity of about 3 wt % to about 9 wt %.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of co-pending U.S. patentapplication Ser. No. 16/302,245, filed on Nov. 16, 2018, which is aNational Stage application under 35 U.S.C. § 371 of PCT/US2017/034585,filed on May 25, 2017, and published as WO 2017/205698, which claimspriority to U.S. Provisional Patent Application No. 62/341,717, filed onMay 26, 2016, which are all incorporated by reference herein.

FIELD

Embodiments described generally relate to binders, resinated furnishes,and methods for making composite products. More particularly, suchembodiments relate to binders containing an aldehyde-based resin, e.g.,a urea-modified aldehyde-based resin, and an isocyanate-based resin,resinated furnishes containing such binders, methods for making suchbinders, and methods for making composite lignocellulose productstherefrom.

BACKGROUND

Binders are used in the production of composite lignocellulose productsto bond lignocellulose substrates to one another. Typical compositelignocellulose products are plywood, oriented strand board (OSB),particleboard, and fiberboard that are made from discrete sheets,veneers, particulates, fibers, or other lignocellulose materials bondedtogether using a binder composition.

Lignocellulose substrates have a moisture content and if the moisturecontent of the lignocellulose substrates is too high, the adhesionbetween the substrates is compromised and failure of the resultingcomposite product is eminent. Accordingly, the lignocellulose substratesused to form composite lignocellulose products are typically dried tohave a moisture content of less than 9 wt %, prior to combining with abinder composition.

The pot life of the binder also affects the quality and reliability ofthe resulting composite lignocellulose product. The pot life of thebinder refers to the time required for the binder to cure. Typicalbinders have a pot life from a few minutes to up to about two to threehours. Thereafter, the viscosity of the binder is generally too high toapply and/or adhere to the lignocellulose substrates. As such, binderswith a short pot life require the frequent preparation of batches ofbinder because those binders must be used in a relatively short amountof time. Additionally, binders with a short pot life are more prone tobeing wasted if a process upset is encountered that prevents the binderfrom being used quickly enough.

There is a need, therefore, for improved binders for making compositelignocellulose products that have a relatively long pot life and thatcan be used with lignocellulose substrates having a water content of 10wt % or more.

SUMMARY

Binders, resinated furnishes, and methods for making compositelignocellulose products therefrom are provided. In one or moreembodiments, a binder for making composite lignocellulose products caninclude about 30 wt % to about 40 wt % of solids that include aurea-modified aldehyde-based resin; about 0.1 wt % to about 3 wt % ofsolids that include an isocyanate-based resin; about 0.1 wt % to about12 wt % of an extender; and about 50 wt % to about 62 wt % of a liquidmedium, where all weight percent values are based on a total weight ofthe binder. The binder can have a sodium hydroxide equivalent weightalkalinity of about 3 wt % to about 9 wt %.

In one or more embodiments, a method for making a composite product caninclude combining a plurality of lignocellulose substrates and a binderto produce a resinated furnish. The binder can include about 30 wt % toabout 40 wt % of solids comprising a urea-modified aldehyde-based resin;about 0.1 wt % to about 3 wt % of solids that include anisocyanate-based resin; about 0.1 wt % to about 12 wt % of an extender;and about 50 wt % to about 62 wt % of a liquid medium, where all weightpercent values are based on a total weight of the binder. The binder canhave a sodium hydroxide equivalent weight alkalinity of about 3 wt % toabout 9 wt %. The method can also include heating the resinated furnishto a temperature of about 60° C. to about 300° C. to at least partiallycure the binder to produce a composite lignocellulose product.

In one or more embodiments, a method for making a binder can includecontacting solids that can include a urea-modified aldehyde-based resin,an isocyanate-based resin, an extender, and a liquid medium to producethe binder. The binder can include about 30 wt % to about 40 wt % ofsolids that include the urea-modified aldehyde-based resin; about 0.1 wt% to about 3 wt % of solids that include the isocyanate-based resin;about 0.1 wt % to about 12 wt % of the extender; and about 50 wt % toabout 62 wt % of the liquid medium, where all weight percent values arebased on a total weight of the binder. The binder can have a sodiumhydroxide equivalent weight alkalinity of about 3 wt % to about 9 wt %.

DETAILED DESCRIPTION

It has been surprisingly and unexpectedly discovered that a binderincluding solids that include one or more urea-modified aldehyde-basedresins, solids that include one or more isocyanate-based resins, one ormore extenders, and a liquid medium, and optionally one or more fillerscan have a viscosity of ≤10,000 cP, ≤6,000 cP, ≤3,500 cP, or ≤2,500 cPwhen maintained at a temperature of about 25° C. for at least the first12 hours, at least 1 day, at least 2 days, or at least 3 days to about 5days, about 10 days, about 15 days, about 20 days, about 25 days, about30 days, or longer upon formation of the binder. The binder can have asodium hydroxide equivalent weight alkalinity of about 3 wt % to about 9wt %. In some embodiments, the binder can have a viscosity of about 200cP to about 3,500 cP when maintained at a temperature of about 25° C.for at least 1 day, at least 3 days, at least 5 days, at least 10 days,at least 15 days, or at least 23 days after formation of the binder.

In some embodiments, one or more first base compounds can be mixed,blended, or otherwise combined with ingredients used to produce theurea-modified aldehyde-based resin. For example, if the urea-modifiedaldehyde-based resin is a phenol-formaldehyde resin, one or more basecompounds can be combined with phenol, formaldehyde, and urea to producea reaction mixture that can be reacted to produce the urea-modifiedaldehyde-based resin. During preparation of the binder, one or moresecond base compounds can be mixed, blended, or otherwise combined withthe urea-modified aldehyde-based resin, the isocyanate-based resin, theone or more extenders, and the liquid medium to produce the binder. Whenthe first base compound and/or the second base compound, if present,include one or more base compounds different from sodium hydroxide, thealkalinity content is proportionally equivalent on a molar weight basis.For example, to attain a 4% sodium hydroxide equivalent weightalkalinity content, 4 grams of sodium hydroxide in 100 grams of thebinder is required, but 5.61 grams of potassium hydroxide in 100 gramsof the binder are required to attain the same alkalinity content.

Without wishing to be bound by theory, it is believed that theurea-modified aldehyde-based resin can include free urea, mono-methylolurea, di-methylol urea, tri-methylol urea, and/or urea reacted into thealdehyde-based resin. In some embodiments, when the urea is reacted intothe aldehyde-based resin, at least a portion of the urea in theurea-modified aldehyde-based resin can be covalently bonded with acarbon atom derived from the aldehyde during synthesis of theurea-modified aldehyde-based resin. Without wishing to be bound bytheory, it is believed that additional stability of the binder in termsof viscosity, i.e., the viscosity of the binder increases at anacceptably slow rate over time, may be the result of the urea-modifiedaldehyde-based resin reacting or otherwise interacting or engaging insome manner with the isocyanate-based resin so that there is less orperhaps even no isocyanate-based resin available to react with water,alcohols, ethers, and/or organic solvents that can be present in thebinder. Also, without wishing to be bound by theory, it is believed thatthe free urea, the mono-methylol urea, the di-methylol urea, and/or thetri-methylol urea may react with isocyanate functional groups of theisocyanate-based resin at a faster rate than water, alcohols, ethers,and/or organic solvents that can be present in the binder, therebyforming polyureas that have a relatively stable viscosity in the binder.The viscosity stability of the binder can provide many technicaladvantages in the manufacture of composite lignocellulose products.

One technical advantage of the binder described herein can be realizedin the production of the binder because neither the urea-modifiedaldehyde-based resin, e.g., a urea-modified phenol-formaldehyde resin,nor the isocyanate-based resin, e.g., polymeric methylene diphenyldiisocyanate, need to be blocked or protected. As such, the additionalsteps required to block or protect the resins to reduce or preventchemical reaction therebetween can be avoided. The unprotected orunblocked urea-modified aldehyde-based resin and/or the unprotected orunblocked isocyanate-based resin can be free or substantially free fromany modification, e.g., chemical modification, which can be added toprotect the functional groups in the respective resins. An example, of aprotected phenol-formaldehyde resin can include the acylatedphenol-formaldehyde resin discussed and described in U.S. Pat. No.6,478,998. The aldehyde-based resin discussed and described herein canbe a non-acylated aldehyde-based resin. In some embodiments, theurea-modified aldehyde-based resin and the isocyanate-based resindescribed herein can be free of or substantially free of any intentionalchemical modification intended to protect or block the functionalgroup(s) thereof. Said another way, the urea-modified aldehyde-basedresin and the isocyanate-based resin described herein can be free orsubstantially free of any protected groups that can be deprotected underreactive conditions, e.g., heat, electromagnetic radiation, or othercondition(s) that can cause or promote chemical reactions.

Another technical advantage of the binder discussed and described hereincan be that the application of the binder, e.g., via spraying, brushing,spreading, coating, dipping, or otherwise contacting, to thelignocellulose substrates as a single homogeneous or substantiallyhomogeneous binder. As such, the urea-modified aldehyde-based resin andthe isocyanate-based resin do not need to be applied separately to thelignocellulose substrates, which can lead to a non-uniform distributionof the urea-modified aldehyde-based resin and/or the isocyanate-basedabout the lignocellulose substrates.

Another technical advantage can be that the binder can be sufficientlyviscosity stable for an adequate length of time to allow large batchesof the binder to be prepared and stored in tanks or other containers andused as needed during the manufacture of composite lignocelluloseproducts.

The binder can include about 30 wt %, about 30.5 wt %, about 31 wt %,about 31.5 wt %, about 32 wt %, about 32.5 wt %, about 33 wt %, about33.5 wt %, or about 34 wt % to about 35 wt %, about 35.5 wt %, about 36wt %, about 36.5 wt %, about 37 wt %, about 37.5 wt %, about 38 wt %,about 38.5 wt %, about 39 wt %, about 39.5 wt %, or about 40 wt % ofsolids that include the urea-modified aldehyde-based resin, based on thetotal weight of the binder. The solids that include the urea-modifiedaldehyde-based resin include solids contributed by all components oringredients used to produce the urea-modified aldehyde-based resin. Forexample, if the urea-modified aldehyde-based resin is a urea-modifiedphenol-formaldehyde resin, the solids that include the urea-modifiedphenol-formaldehyde resin include phenol, formaldehyde, urea, a firstbase compound, and any optional additional components or ingredients,e.g., a salt, that can be mixed, blended, or otherwise combined with oneanother and at least partially reacted to produce the urea-modifiedphenol-formaldehyde resin.

The binder can include about 0.1 wt %, about 0.3 wt %, about 0.5 wt %,about 0.7 wt %, or about 1 wt % to about 1.5 wt %, about 1.7 wt %, about2 wt %, about 2.3 wt %, about 2.5 wt %, about 2.7 wt %, or about 3 wt %of solids that include the isocyanate-based resin, based on the totalweight of the binder. The binder can include about 0.1 wt %, about 0.3wt %, about 0.5 wt %, about 0.7 wt %, about 1 wt %, about 1.5 wt %,about 2 wt %, about 2.5 wt %, or about 3 wt % to about 5 wt %, about 6wt %, about 7 wt %, about 8 wt %, about 9 wt %, about 10 wt %, about 11wt %, about 12 wt %, about 13 wt %, about 14 wt %, or about 15 wt % ofthe extender, based on the total weight of the binder. The binder canalso include about 45 wt %, about 47 wt %, about 50 wt %, about 52 wt %,or about 55 wt % to about 56 wt %, about 58 wt %, about 60 wt %, about62 wt %, or about 64 wt % of a liquid medium, based on the total weightof the binder. In some embodiments, the binder can optionally includeabout 0.1 wt %, about 0.3 wt %, about 0.5 wt %, about 0.7 wt %, about 1wt %, about 1.5 wt %, about 2 wt %, about 2.5 wt %, or about 3 wt % toabout 5 wt %, about 6 wt %, about 7 wt %, about 8 wt %, about 9 wt %,about 10 wt %, about 11 wt %, about 12 wt %, about 13 wt %, about 14 wt%, or about 15 wt % of a filler, based on the total weight of thebinder. In some embodiments, the binder can include about 30 wt % toabout 40 wt % of solids that include the urea-modified aldehyde-basedresin, about 0.1 wt % to about 3 wt % of solids that include theisocyanate-based resin, about 0.1 wt % to about 15 wt % of the extender,about 45 wt % to about 64 wt % of the liquid medium, and optionally,about 0.1 wt % to about 15 wt % of the filler, where all weight percentvalues are based on the total weight of the binder.

The binder can have a sodium hydroxide equivalent weight alkalinity ofabout 3 wt %, about 3.3 wt %, about 3.5 wt %, about 3.7 wt %, about 4 wt%, about 4.3 wt %, about 4.5 wt %, about 4.7 wt %, or about 5 wt % toabout 6 wt %, about 6.3 wt %, about 6.5 wt %, about 6.7 wt %, about 7 wt%, about 7.3 wt %, about 7.5 wt %, about 7.7 wt %, about 8 wt %, about8.3 wt %, about 8.5 wt %, about 8.7 wt %, or about 9 wt %. In someembodiments, the binder can have a sodium hydroxide equivalent weightalkalinity of at least 3 wt %, at least 3.3 wt %, at least 3.5 wt %, atleast 3.7 wt %, at least 4 wt %, at least 4.3 wt %, at least 4.5 wt %,at least 4.7 wt %, at least 5 wt %, at least 5.3 wt % or at least 5.5 wt% to less than 9 wt %, less than 8.5 wt %, less than 8 wt %, less than7.5 wt %, or less than 7 wt %.

The binder can include about 0.1 wt %, about 0.5 wt %, about 1 wt %,about 1.5 wt %, about 2 wt %, about 2.5 wt %, about 3 wt %, about 3.5 wt%, or about 4 wt % to about 6 wt %, about 6.5 wt %, about 7 wt %, about7.5 wt %, about 8 wt %, about 8.5 wt %, about 9 wt %, about 9.3 wt %, orabout 9.5 wt % of urea, whether the urea be in the form of free urea,mono-methylol urea, di-methylol urea (symmetrical and/or asymmetrical),tri-methylol urea, urea reacted into the aldehyde-based resin, or anycombination thereof, based on the total weight of the binder. In someembodiments, the binder can include about 30 wt % to about 40 wt % ofsolids that include the urea-modified aldehyde-based resin, about 0.1 wt% to about 3 wt % of solids that include the isocyanate-based resin,about 0.1 wt % to about 15 wt % of the extender, about 45 wt % to about64 wt % of the liquid medium, about 0.1 wt % to about 9.5 wt % of urea,whether the urea be in the form of free urea, mono-methylol urea,di-methylol urea, tri-methylol urea, urea reacted into thealdehyde-based resin, or any combination thereof, and optionally, about0.1 wt % to about 15 wt % of the filler, where all weight percent valuesare based on the total weight of the binder.

In some embodiments, the binder can have a percent of total mix solidsof about 40 wt %, about 41 wt %, about 42 wt %, about 43 wt %, or about44 wt % to about 44.5 wt %, about 45 wt %, about 46 wt %, about 47 wt %,or about 48 wt %, based on the total weight of the binder. The terms“percent of total mix solids” or “% Total Mix Solids” refer to the sumof all solids in the binder, such as solids contributed from theurea-modified aldehyde-based resin, the isocyanate-based resin, theextender, any second base compound, the optional filler, and any otheroptional components that can be included in the binder. In someembodiments, the binder can have a mix resin solids or MRS of about 27wt %, about 28 wt %, about 29 wt %, about 30 wt %, about 31 wt %, about32 wt %, or about 33 wt % to about 35 wt %, about 36 wt %, about 37 wt%, about 38 wt %, about 39 wt %, or about 40 wt %, based on the totalweight of the binder. The terms “mix resin solids” and “MRS” refer tothe total amount of solids contributed by the urea-modifiedaldehyde-based resin and the isocyanate-based resin. The MRS includessolids contributed by all components used to produce the urea-modifiedaldehyde-based resin. For example, if the urea-modified aldehyde-basedresin includes a urea-modified phenol-formaldehyde resin, the MRS solidsfrom the urea-modified phenol-formaldehyde resin include the phenol, theformaldehyde, the first base compound, the urea, and any optionaladditional compounds such as a salt that can be combined and at leastpartially reacted to produce the urea-modified phenol-formaldehyderesin.

In some embodiments, the binder can include about 71 wt % to about 99.7wt % of at least one urea-modified aldehyde-based resin, about 0.3 wt %to about 29 wt % of at least one isocyanate-based resin, about 10 wt %to about 58 wt % of at least one extender, and about 145 wt % to about230 wt % of liquid medium, where all weight percent values are based ona combined solids weight of the urea-modified aldehyde-based resin andthe isocyanate-based resin. In some embodiments, the binder can includeabout 0.5 wt %, about 2 wt %, or about 4 wt % to about 6 wt %, about 8wt %, or about 10 wt % of urea, mono-methylol urea, di-methylol urea,tri-methylol urea, urea reacted into the aldehyde-based resin, or anycombination thereof, based on the combined solids weight of theurea-modified aldehyde-based resin and the isocyanate-based resin.

It has also been surprisingly and unexpectedly discovered that aplurality of lignocellulose substrates that have a water content ofabout 9 wt %, about 10 wt %, about 11 wt %, about 12 wt %, about 13 wt%, or about 14 wt % to about 16 wt %, about 20 wt %, about 30 wt %, orabout 40 wt %, based on a dried weight of the lignocellulose substrates,can be bonded to one another with the binder described herein. Suchbinder can provide a composite product that is better than a comparativecomposite product made with the same lignocellulose substrates, but at awater content of less than 10 wt %, and with the same urea-modifiedaldehyde-based resin, but without the isocyanate-based resin.Accordingly, another significant technical advantage of the binder canbe the manufacture of composite lignocellulose products fromlignocellulose substrates having a relatively high moistureconcentration that can be present when the binder is at least partiallycured rather than having to remove the moisture from the lignocellulosesubstrates prior to application of the binder thereto. Significant timeand energy savings can be realized by being able to manufacturecomposite lignocellulose products with lignocellulose substrates havinga moisture or water content of at least 9 wt %, at least 10 wt %, atleast 11 wt %, at least 12 wt %, at least 15 wt %, at least 18 wt %, orat least 20 wt % to about 40 wt %, based on the dried weight of thelignocellulose substrates.

The lignocellulose substrate(s) and the binder can be mixed, blended, orotherwise combined to produce a mixture or “resinated furnish”. Thebinder in the resinated furnish can be at least partially cured. Forexample, the resinated furnish can be heated to at least partially curethe binder. The at least partially cured binder can adhere or otherwisebond the plurality of lignocellulose substrates to one another toprovide a composite product. In some embodiments, the lignocellulosesubstrate can have a water content of 10 wt % to about 40 wt %, based ona dried weight of the lignocellulose substrate at the time the binder iscombined therewith. In some embodiments, the lignocellulose substratecan have a water content of 10 wt % to about 40 wt % when or during thetime the binder is at least partially cured. For example, if the binderis at least partially cured by heating the resinated furnish to atemperature of about 60° C. to about 300° C., the lignocellulosesubstrate can have a water content of 10 wt % to about 40 wt % when theresinated furnish is heated to a temperature of about 60° C. or more.

In some embodiments, the binder can have a viscosity of about 200 cP,about 700 cP, or about 1,000 cP to about 3,500 cP, about 5,000 cP, about7,500 cP, or about 10,000 cP at a temperature of about 25° C. whencombined with the plurality of lignocellulose substrates to produce theresinated furnish. In some embodiments, the binder can be combined withthe plurality of lignocellulose substrates at least 1 hour, at least 2hours, at least 3 hours, at least 6 hours, at least 12 hours, at least18 hours, at least 24 hours, at least 30 hours, at least 36 hours, atleast 42 hours, at least 48 hours, or longer after at least theurea-modified aldehyde-based resin, the isocyanate-based resin, theextender, the liquid medium, and, if present, any additional ingredientswere combined to produce the binder. In other embodiments, the bindercan be combined with the plurality of lignocellulose substrates about 1day, about 2 days, about 3 days, about 4 days, about 5 days, about 6days, or about 7 days to about 10 days, about 15 days, about 20 days,about 25 days, about 30 days, or longer after at least the urea-modifiedaldehyde-based resin, the isocyanate-based resin, the extender, theliquid medium, and, if present, any additional ingredients were combinedto produce the binder. In some embodiments, the additional ingredientscan be or can include, but are not limited to, one or more fillers, oneor more surfactants, one or more salts, and/or other compounds discussedand described below.

The aldehyde-based resin can be or include, but is not limited to, oneor more of: phenol-formaldehyde (PF) resin, phenol-urea-formaldehyde(PUF) resin, melamine-formaldehyde (MF) resin,melamine-urea-formaldehyde (MUF) resin, phenol-melamine-formaldehyde(PMF) resin, urea-formaldehyde (UF) resin, resorcinol-formaldehyde (RF)resin, phenol-resorcinol-formaldehyde (PRF) resin, copolymers thereof,isomers thereof, or any mixture thereof. In some embodiments, thealdehyde-based resin can include one or more phenol-formaldehyde resins,one or more urea-formaldehyde resins, one or morephenol-urea-formaldehyde resins, or any mixture thereof. For example,urea and a phenol-formaldehyde resin can be combined, phenol and aurea-formaldehyde resin can be combined, or phenol, urea, andformaldehyde can be combined to make a phenol-urea-formaldehyde resin.Suitable methods for synthesizing the urea-modified aldehyde-based resincan include both single step processes and multi-step or “programmed”processes such as a staged monomer/catalyst addition process. Whilebatch operations are generally the standard, continuous processes canalso be used.

The aldehyde compound in the urea-modified aldehyde-based resin can beor include one or more substituted aldehyde compounds, one or moreunsubstituted aldehyde compounds, or any mixture thereof. Illustrativealdehyde compounds can include, but are not limited to, aldehydes havingthe chemical formula RCHO, where R is hydrogen or a hydrocarbyl group.Illustrative hydrocarbyl groups can include 1 carbon atom to about 8carbon atoms. Suitable aldehyde compounds can also include the so-calledmasked aldehydes or aldehyde equivalents, such as acetals orhemiacetals. Specific aldehyde compounds can include, but are notlimited to, formaldehyde, paraformaldehyde, cinnamaldehyde,tolualdehyde, acetaldehyde, propionaldehyde, butyraldehyde, furfural,benzaldehyde, retinaldehyde, glyoxal, malondialdehyde, succindialdehyde,glutaraldehyde, phthaldehyde, derivatives thereof, or any mixturethereof. Still other suitable formaldehyde compounds can includeformaldehyde present in a prepolymer or precondensate, such asurea-formaldehyde condensate (UFC) or UF precondensate. In at least oneembodiment, the aldehyde compound can be or include formaldehyde.

The phenolic compound, when used to produce the urea-modifiedaldehyde-based resin, can be or include phenol (also known asmonohydroxybenzene), one or more substituted phenol compounds, or anycombination or mixture thereof. Illustrative substituted phenolcompounds can include, but are not limited to, alkyl-substituted phenolssuch as the cresols and xylenols; cycloalkyl-substituted phenols such ascyclohexyl phenol; alkenyl-substituted phenols; aryl-substituted phenolssuch as p-phenyl phenol; alkoxy-substituted phenols such as3,5-dimethyoxyphenol; aryloxy phenols such as p-phenoxy phenol;halogen-substituted phenols such as p-chlorophenol, or any mixturethereof. Dihydric phenols such as catechol, resorcinol, hydroquinone,bisphenol A and bisphenol F also can also be used. In some embodiments,the phenolic compound can be or can include, but is not limited to,resorcinol, phenol, catechol, hydroquinone, pyrogallol,5-methylresorcinol, 5-ethylresorcinol, 5-propylresorcinol,4-methylresorcinol, 4-ethylresorcinol, 4-propylresorcinol, resorcinolmonobenzoate, resorcinol monosinate, resorcinol diphenyl ether,resorcinol monomethyl ether, resorcinol monoacetate, resorcinol dimethylether, phloroglucinol, benzoylresorcinol, resorcinol rosinate, alkylsubstituted resorcinol, aralkyl substituted resorcinol,2-methylresorcinol, phloroglucinol, 1,2,4-benzenetriol,3,5-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 4-ethylresorcinol,2,5-dimethylresorcinol, 5-methylbenzene-1,2,3-triol, 3,5-dihydroxybenzylalcohol, 2,4,6-trihydroxytoluene, 4-chlororesorcinol,2′,6′-dihydroxyacetophenone, 2′,4′-dihydroxyacetophenone,3′,5′-dihydroxyacetophenone, 2,4,5-trihydroxybenzaldehyde,2,3,4-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde,3,5-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid,2,6-dihydroxybenzoic acid, 1,3-dihydroxynaphthalene,2′,4′-dihydroxypropiophenone, 2′,4′-dihydroxy-6′-methylacetophenone,1-(2,6-dihydroxy-3-methylphenyl)ethanone, 3-methyl3,5-dihydroxybenzoate, methyl 2,4-dihydroxybenzoate, gallacetophenone,2,4-dihydroxy-3-methylbenzoic acid, 2,6-dihydroxy-4-methylbenzoic acid,methyl 2,6-dihydroxybenzoate, 2-methyl-4-nitroresorcinol,2,4,5-trihydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid,2,3,4-trihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid,2-nitrophloroglucinol, or any mixture thereof. In at least oneembodiment, the urea-modified aldehyde-based resin can be or includephenol, resorcinol, or a mixture thereof.

The urea component of the urea-modified aldehyde-based resin can beprovided in many forms. For example, solid urea, such as prill, and/orurea solutions, typically aqueous solutions, are commonly available.Further, the urea component can be combined with another moiety, forexample, formaldehyde and/or urea-formaldehyde adducts, often in aqueoussolution. Any form of urea or urea in combination with formaldehyde (orother aldehyde(s)) can be used to make the urea-modified aldehyde-basedresin. Both urea prill and combined urea-aldehyde products can be used.Illustrative urea-formaldehyde products can include, but are not limitedto, Urea Formaldehyde (UFC). These types of products can include thosedescribed in U.S. Pat. Nos. 5,362,842 and 5,389,716, for example.

The urea-modified aldehyde-based resin can be a thermosetting resin. Forexample, if the urea-modified aldehyde-based resin includes aphenol-formaldehyde resin, the phenol-formaldehyde resin can be aphenol-formaldehyde resole resin having a molar ratio of formaldehyde tophenol of 1 or greater. The urea-modified aldehyde-based resin can be athermoplastic resin. For example, if the urea-modified aldehyde-basedresin includes a phenol-formaldehyde resin, the phenol-formaldehyderesin can be a phenol-formaldehyde novolac resin having a molar ratio offormaldehyde to phenol of less than 1. Phenol-formaldehyde resins thatcan be used to make the binder can include a phenol-formaldehyde resin,such as GPR 5815, GPR 5814, GPR 5812, and/or GPR 5772 resins, which arecommercially available from Georgia-Pacific Chemicals LLC in SouthAmerica, a phenol-formaldehyde resin powder, such as WOODWELD® 190C42spray-dried OSB adhesive, commercially available from Georgia-PacificChemicals LLC, or a mixture thereof.

Considering phenolic-aldehyde resole resins in particular, a molar ratioof the aldehyde compound to the phenolic compound in thephenolic-aldehyde resole resin can be about 1.05:1, about 1.1:1, about1.2:1, about 1.4:1, about 1.6:1, about 1.8:1, or about 2:1 to about1.2:1, about 2.5:1, about 2.7:1, about 3:1, about 3.5:1, or about 4:1.In some embodiments, the molar ratio of the aldehyde compound to thephenolic compound in the phenolic-aldehyde resole resin can be about1.5:1 to about 3:1, about 1.9:1 to about 2.6:1, about 2:1 to about2.5:1, about 2.1:1 to about 2.6:1, about 2.2:1 to about 2.5:1, or about2.3:1 to about 2.5:1. In some embodiments, the urea-modifiedaldehyde-based resin can be or can include a phenol-formaldehyde resinhaving a formaldehyde to phenol molar ratio of about 1.05:1, about1.1:1, about 1.2:1, about 1.4:1, about 1.6:1, about 1.8:1, about 1.9:1,about 2:1, about 2.1:1, or about 2.2:1 to about 2.3:1, about 2.4:1,about 2.5:1, about 2.6:1, about 2.7:1, about 3:1, about 3.5:1, or about4:1.

Considering phenolic-urea-aldehyde resins in particular, a molar ratioof the aldehyde compound to the phenolic compound in thephenol-urea-aldehyde resin can be about 1.05:1, about 1.1:1, about1.2:1, about 1.4:1, about 1.6:1, about 1.8:1, or about 2:1 to about1.2:1, about 2.5:1, about 2.7:1, about 3:1, about 3.5:1, or about 4:1.In some embodiments, the molar ratio of the aldehyde compound to thephenolic compound in the phenol-urea-aldehyde resin can be about 1.5:1to about 3:1, about 1.9:1 to about 2.6:1, about 2:1 to about 2.5:1,about 2.1:1 to about 2.6:1, about 2.2:1 to about 2.5:1, or about 2.3:1to about 2.5:1. In some embodiments, the urea-modified aldehyde-basedresin can be or can include a phenol-urea-formaldehyde resin having aformaldehyde to phenol molar ratio of about 1.2:1, about 1.4:1, about1.6:1, about 1.8:1, about 1.9:1, about 2:1, about 2.1:1, or about 2.2:1to about 2.3:1, about 2.4:1, about 2.5:1, about 2.6:1, about 2.7:1,about 3:1, about 3.5:1, or about 4:1. In some embodiments, thephenol-urea-aldehyde resin can have a formaldehyde to urea molar ratioof about 3.7:1, about 3.9:1, about 4:1, about 4.5:1, or about 5:1 toabout 7:1, about 8.5:1, about 20:1, about 40:1, about 60:1, about73.5:1, about 100:1, about 120:1, about 130:1, about 140:1, about 147:1,or about 150:1. In some embodiments, the phenol-urea-aldehyde resin canhave a phenol to urea molar ratio of about 1.5:1, about 1.7:1, about2:1, or about 3:1 to about 3.8:1, about 10:1, about 40:1, about 50:1,about 65.4:1, about 100:1, about 125:1, about 150:1, or about 163.4:1.

In some embodiments, the binder can include about 0.1 wt %, about 0.5 wt%, about 1 wt %, about 1.5 wt %, about 2 wt %, about 2.5 wt %, about 3wt %, about 3.5 wt %, or about 4 wt % to about 6 wt %, about 6.5 wt %,about 7 wt %, about 7.5 wt %, about 8 wt %, about 8.5 wt %, about 9 wt%, about 9.3 wt %, or about 9.5 wt % of urea, whether the urea is in theform of free urea, mono-methylol urea, di-methylol urea, tri-methylolurea, urea reacted into the aldehyde-based resin, or any mixturethereof, based on the total weight of the binder. In some embodiments,the urea-modified aldehyde-based resin can include at least 0.5 wt %, atleast 1 wt %, at least 1.5 wt %, at least 2 wt %, at least 2.5 wt %, atleast 3 wt %, at least 3.5 wt %, at least 4 wt %, at least 4.5 wt %, atleast 5 wt %, at least 6 wt %, at least 6.5 wt %, at least 7 wt %, atleast 7.5 wt %, or at least 8 wt % of urea, whether the urea is in theform of free urea, mono-methylol urea, di-methylol urea, tri-methylolurea, urea reacted into the aldehyde-based resin, or any mixturethereof, based on the total weight of the urea-modified aldehyde-basedresin. In some embodiments, the urea-modified aldehyde-based resin, on asolids basis, can include about 3.5 wt %, about 4 wt %, about 4.5 wt %,about 5 wt %, about 7 wt %, about 10 wt %, or about 12 wt % to about 15wt %, about 16 wt %, about 17 wt %, about 18 wt %, about 19 wt %, about20 wt %, about 23 wt %, or about 27 wt % of urea, whether the urea is inthe form of free urea, mono-methylol urea, di-methylol urea,tri-methylol urea, urea reacted into the aldehyde-based resin, or anymixture thereof. In some embodiments, the urea-modified aldehyde-basedresin can include about 0.1 wt %, about 0.5 wt %, about 2 wt %, or about4 wt % to about 6 wt %, about 8 wt %, or about 10 wt % of urea, whetherthe urea is in the form of free urea, mono-methylol urea, di-methylolurea, tri-methylol urea, urea reacted into the aldehyde-based resin, orany combination thereof, based on a combined solids weight of theurea-modified aldehyde-based resin and the isocyanate-based resin.

In some embodiments, the urea-modified aldehyde-based resin can includea mixture of at least one of: a phenol-formaldehyde resin, aurea-formaldehyde resin, a phenol-urea-formaldehyde resin, amelamine-formaldehyde resin, a melamine-urea-formaldehyde resin, aphenol-melamine-formaldehyde resin, a resorcinol-formaldehyde resin, anda phenol-resorcinol-formaldehyde resin, and at least one of free urea,mono-methylol urea, di-methylol urea, and tri-methylol urea. In someembodiments, the urea-modified aldehyde-based resin can be or caninclude a phenol-urea-formaldehyde resin. In some embodiments, all or atleast a portion of the urea in the urea-modified aldehyde-based resincan be covalently bonded with a carbon atom derived from the aldehydeduring synthesis of the urea-modified aldehyde-based resin, e.g., aphenol-urea-formaldehyde resin. As such, in some embodiments, at least aportion of the urea in the urea-modified aldehyde-based resin can becovalently bonded with a carbon atom derived from the aldehyde duringsynthesis of the urea-modified aldehyde-based resin, e.g., aphenol-urea-formaldehyde resin, and the urea-modified aldehyde-basedresin can also include at least one of free urea, mono-methylol urea,di-methylol urea, and tri-methylol urea.

The first and second base compounds can independently be or canindependently include, but are not limited to, one or more hydroxides,one or more carbonates, ammonia, one or more amines, one or moreborates, or any mixture thereof. Illustrative hydroxides can include,but are not limited to, sodium hydroxide, potassium hydroxide, ammoniumhydroxide (e.g., aqueous ammonia), lithium hydroxide, calcium hydroxide,and cesium hydroxide. Illustrative carbonates can be or include, but arenot limited to, sodium carbonate, sodium bicarbonate, potassiumcarbonate, calcium carbonate, and ammonium carbonate. Illustrativeamines can include, but are not limited to, trimethylamine,triethylamine, triethanolamine, diisopropylethylamine (Hunig's base),pyridine, 4-dimethylaminopyridine (DMAP), and1,4-diazabicyclo[2.2.2]octane (DABCO). Illustrative borates can include,but are not limited to, sodium borate, potassium borate, calcium borate,and zinc borate. The alkaline reagent can be used to adjust the pH ofthe binder.

In some embodiments, the binder can include about 3 wt %, about 3.5 wt%, about 4 wt %, about 4.5 wt %, about 5 wt %, or about 5.5 wt % toabout 6 wt %, about 6.5 wt %, about 7 wt %, about 7.5 wt %, about 8 wt%, about 8.5 wt %, or about 9 wt % of the base compound(s), i.e., anyfirst base compound and any second base compound, based on the totalweight of the binder. In some embodiments, the urea-modifiedaldehyde-based resin can include about 0.05 wt %, about 0.1 wt %, about0.3 wt %, about 0.5 wt %, about 0.7 wt %, about 1 wt %, about 2 wt %, orabout 2.5 wt % to about 3 wt %, about 3.5 wt %, about 4 wt %, about 4.5wt %, about 4.8 wt %, about 5 wt %, about 6 wt %, or about 8 wt % of thefirst base compound, based on the combined solids weight of theurea-modified aldehyde-based resin and the isocyanate-based resin. Inother embodiments, the binder can include the base compound(s), i.e.,any first base compound and any second base compound, in an amount ofabout 0.5 wt % to about 8 wt %, about 0.5 wt % to about 6 wt %, about0.5 wt % to about 5 wt %, about 0.5 wt % to about 4 wt %, about 0.5 wt %to about 3.5 wt %, about 0.5 wt % to about 3 wt %, about 1 wt % to about8 wt %, about 1 wt % to about 6 wt %, about 1 wt % to about 5 wt %,about 1 wt % to about 4 wt %, about 1 wt % to about 3.5 wt %, about 1 wt% to about 3 wt %, about 2 wt % to about 8 wt %, about 2 wt % to about 6wt %, about 2 wt % to about 5 wt %, about 2 wt % to about 4 wt %, about2 wt % to about 3.5 wt %, about 2 wt % to about 3 wt %, about 2.5 wt %to about 8 wt %, about 2.5 wt % to about 6 wt %, about 2.5 wt % to about5 wt %, about 2.5 wt % to about 4 wt %, about 2.5 wt % to about 3.5 wt%, or about 2.5 wt % to about 3 wt %, based on the combined solidsweight of the urea-modified aldehyde-based resin and theisocyanate-based resin.

In some embodiments, the urea-modified aldehyde-based resin can be inthe form of a solution, dispersion, suspension, or other mixture. Forexample, the urea-modified aldehyde-based resin can include water,alcohol(s), ether(s), and/or other organic solvents. In some embodiment,the urea-modified aldehyde-based resin, if in the form of a solution,dispersion, suspension, or other mixture, can have a solids content ofabout 20 wt %, about 25 wt %, about 30 wt %, about 35 wt %, or about 40wt % to about 45 wt %, about 50 wt %, about 55 wt %, about 60 wt %,about 70 wt %, about 80 wt %, about 90 wt %, or about 95 wt %, based ona total weight of the urea-modified aldehyde-based resin. In otherembodiments, the urea-modified aldehyde-based resin can have a solidscontent of about 35 wt % to about 55 wt %, about 40 wt % to about 50 wt%, about 41 wt % to about 47 wt %, about 42 wt % to about 46 wt %, orabout 43 wt % to about 45 wt %, based on a total weight of theurea-modified aldehyde-based resin.

As used herein, the terms “solids weight”, “solids concentration”, and“solids content” of a liquid solution, dispersion, suspension, or othermixture, e.g., an aqueous urea-modified aldehyde-based resin, asunderstood by those skilled in the art, can be measured by determiningthe weight loss upon heating about 1 gram of the mixture to atemperature of about 125° C. for a time period of about 1 hour and 45minutes in triplicate and then then three results can be averagedtogether. By measuring the weight of the sample before and afterheating, the percent solids in the sample can be directly calculated orotherwise estimated.

If the urea-modified aldehyde-based resin is mixed, blended, orotherwise includes any water, alcohol, ether, and/or one or more otherorganic solvents, the amount of the urea-modified aldehyde-based resinin the binder is discussed in terms of the urea-modified aldehyde-basedresins solids. For example, if 500 grams of an aqueous urea-modifiedaldehyde-based resin that contains about 43.5 wt % of urea-modifiedaldehyde-based resin solids is in a 1,000 gram sample of a binder, the1,000 gram sample of binder would be said to contain about 21.75 wt % ofsolids that include the urea-modified aldehyde-based resin, based on atotal weight of the binder.

The urea-modified aldehyde-based resin, when mixed with water, can forman aqueous solution, dispersion, suspension, or other mixture that canhave a pH of about 7, about 8, about 9, or about 10 to about 11, about12, or about 13 at a temperature of about 25° C. For example, aurea-modified aldehyde-based resin having a water content of about 40 wt% to about 70 wt % can form an aqueous solution, dispersion, suspension,or other mixture that can have a pH of about 8 to about 11, about 9 toabout 10.5, about 9.5 to about 11.5, about 10 to about 12, about 10.5 toabout 12.5, about 10.5 to about 11, about 10.6 to about 12, about 11 toabout 12, or about 11.5 to about 12.5 at a temperature of about 25° C.

In some embodiments, the binder can include about 30 wt %, about 30.5 wt%, about 31 wt %, about 31.5 wt %, about 32 wt %, about 32.5 wt %, about33 wt %, about 33.5 wt %, or about 34 wt % to about 35 wt %, about 35.5wt %, about 36 wt %, about 36.5 wt %, about 37 wt %, about 37.5 wt %,about 38 wt %, about 38.5 wt %, about 39 wt %, about 39.5 wt %, or about40 wt % of solids that include the urea-modified aldehyde-based resin,based on the total weight of the binder. In some embodiments, the bindercan include about 0.1 wt %, about 0.5 wt %, about 1 wt %, about 1.5 wt%, about 2 wt %, about 2.5 wt %, about 3 wt %, about 3.5 wt %, or about4 wt % to about 6 wt %, about 6.5 wt %, about 7 wt %, about 7.5 wt %,about 8 wt %, about 8.5 wt %, about 9 wt %, about 9.3 wt %, or about 9.5wt % of any urea, i.e., free urea, any mono-methylol urea, anydi-methylol urea, any tri-methylol urea, any urea reacted into thealdehyde-based resin, or any combination thereof, based on the totalweight of the binder. In some embodiments, the binder can include theurea-modified aldehyde-based resin in an amount of about 70 wt %, about73 wt %, about 75 wt %, about 77 wt %, about 79 wt %, about 81 wt %,about 83 wt %, or about 85 wt % to about 87 wt %, about 89 wt %, about91 wt %, about 93 wt %, about 95 wt %, about 97 wt %, about 98.5 wt %,about 99.7 wt %, or greater, based on a combined solids weight of theurea-modified aldehyde-based resin and the isocyanate-based resin. Inother embodiments, the binder can include the urea-modifiedaldehyde-based resin in an amount of at least 71 wt %, at least 74 wt %,at least 76 wt %, at least 78 wt %, at least 80 wt %, at least 82 wt %,or at least 84 wt % to about 90 wt %, about 91 wt %, about 92 wt %,about 93 wt %, about 94 wt %, about 95 wt %, about 96 wt %, about 97 wt%, about 98 wt %, about 98.5 wt %, about 99 wt %, about 99.5 wt %, about99.7 wt %, or greater, based on a combined solids weight of theurea-modified aldehyde-based resin and the isocyanate-based resin.

The isocyanate-based resin can be or include, but is not limited to, oneor more of: methylene diphenyl diisocyanate (MDI), polymeric methylenediphenyl diisocyanate (pMDI), emulsified polymer isocyanate (EPI),copolymers thereof, isomers thereof, or any mixture thereof.Illustrative MDI resins and pMDI resins can be or include any one ormore isomers, such as 2,2′-methylene diphenyl diisocyanate (2,2′-MDI),2,4′-methylene diphenyl diisocyanate (2,4′-MDI), 4,4′-methylene diphenyldiisocyanate (4,4′-MDI), or any mixture thereof. In some embodiments,the isocyanate-based resin can be or include pMDI, such as DESMODUR®44V20L resin, commercially available from Covestro.

In some embodiments, the binder can include about 0.1 wt %, about 0.3 wt%, about 0.5 wt %, about 0.7 wt %, or about 1 wt % to about 1.5 wt %,about 1.7 wt %, about 2 wt %, about 2.3 wt %, about 2.5 wt %, about 2.7wt %, or about 3 wt % of the isocyanate-based resin, based on the totalweight of the binder. In some embodiments, the binder can include about0.1 wt %, about 0.3 wt %, about 0.5 wt %, about 0.7 wt %, or about 1 wt% to about 1.5 wt %, about 1.7 wt %, about 2 wt %, about 2.3 wt %, about2.5 wt %, about 2.7 wt %, or about 3 wt % of solids that include theisocyanate-based resin, based on the total weight of the binder. In someembodiments, the binder can include the isocyanate-based resin in anamount of about 0.3 wt %, about 0.5 wt %, about 1 wt %, about 1.5 wt %,about 2 wt %, about 3 wt %, about 4 wt %, about 5 wt %, about 6 wt %,about 7 wt %, about 8 wt %, or about 9 wt % to about 10 wt %, about 11wt %, about 12 wt %, about 13 wt %, about 14 wt %, about 15 wt %, about16 wt %, about 17 wt %, about 18 wt %, about 19 wt %, about 20 wt %,about 21 wt %, about 22 wt %, about 23 wt %, about 24 wt %, about 25 wt%, about 26 wt %, about 27 wt %, about 28 wt %, about 29 wt %, or about30 wt %, based on the combined solids weight of the urea-modifiedaldehyde-based resin and the isocyanate-based resin. In otherembodiments, the binder can include the isocyanate-based resin in anamount of about 0.3 wt %, about 0.5 wt %, about 1 wt %, about 1.5 wt %,about 2 wt %, about 3 wt %, about 4 wt %, about 5 wt %, about 6 wt %,about 7 wt %, about 8 wt %, about 9 wt %, about 10 wt %, about 11 wt %,or about 12 wt % to less than 15 wt %, less than 16 wt %, less than 17wt %, less than 18 wt %, less than 19 wt %, less than 20 wt %, less than21 wt %, less than 22 wt %, less than 23 wt %, less than 24 wt %, orless than 25 wt %, based on the combined solids weight of theurea-modified aldehyde-based resin and the isocyanate-based resin.

In other embodiments, the binder can include the isocyanate-based resinin an amount of about 0.5 wt %, about 1 wt %, about 2 wt %, about 3 wt%, about 4 wt %, about 5 wt %, or about 6 wt % to about 10 wt %, about12 wt %, about 14 wt %, about 16 wt %, about 18 wt %, about 20 wt %, orabout 22 wt %, based on the combined solids weight of the urea-modifiedaldehyde-based resin and the isocyanate-based resin. In otherembodiments, the binder can include the isocyanate-based resin in anamount of about 0.3 wt % to about 28.3 wt %, about 0.5 wt % to about 25wt %, about 1 wt % to about 22 wt %, about 1.5 wt % to about 20.7 wt %,about 3 wt % to about 15 wt %, about 3.3 wt % to about 14.6 wt %, about1.5 wt % to about 10 wt %, about 7 wt % to about 13 wt %, or about 11 wt% to about 15 wt %, based on the combined solids weight of theurea-modified aldehyde-based resin and the isocyanate-based resin.

In some embodiments, the binder can include the urea-modifiedaldehyde-based resin in an amount of about 70 wt % to about 99.7 wt %and the isocyanate-based resin in an amount of about 0.3 wt % to about30 wt %, based on the combined solids weight of the urea-modifiedaldehyde-based resin and the isocyanate-based resin. In otherembodiments, the binder can include the urea-modified aldehyde-basedresin in an amount of about 71.7 wt % to about 99.7 wt % and theisocyanate-based resin in an amount of about 0.3 wt % to about 28.3 wt%, based on the combined solids weight of the urea-modifiedaldehyde-based resin and the isocyanate-based resin. In otherembodiments, the binder can include the urea-modified aldehyde-basedresin in an amount of about 79.3 wt % to about 98.5 wt % and theisocyanate-based resin in an amount of about 1.5 wt % to about 20.7 wt%, based on the combined solids weight of the urea-modifiedaldehyde-based resin and the isocyanate-based resin. In otherembodiments, the binder can include the urea-modified aldehyde-basedresin in an amount of about 85.4 wt % to about 96.7 wt % and theisocyanate-based resin in an amount of about 3.3 wt % to about 14.6 wt%, based on the combined solids weight of the urea-modifiedaldehyde-based resin and the isocyanate-based resin.

Illustrative liquid mediums that the binder can include can be or caninclude, but are not limited to, water, one or more alcohols, one ormore ethers, one or more other organic solvents, or any mixture thereof.In at least one embodiment, the liquid medium can be water. Illustrativealcohols can include, but are not limited to, methanol, ethanol,propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol,ethylene glycol, or any mixture thereof. Illustrative ethers caninclude, but are not limited to, dimethyl ether, diethyl ether,tetrahydrofuran, or any mixture thereof.

In some embodiments, if the binder, prior to curing, includes one ormore liquid mediums (e.g., water), the binder can include about 45 wt %,about 47 wt %, about 50 wt %, about 52 wt %, or about 55 wt % to about56 wt %, about 58 wt %, about 60 wt %, about 62 wt %, or about 64 wt %of the liquid medium, based on the total weight of the binder. In someembodiments, the binder can include about 145 wt %, about 150 wt %,about 155 wt %, about 160 wt %, about 165 wt %, about 170 wt %, about175 wt %, or about 180 wt % to about 190 wt %, about 195 wt %, about 200wt %, about 205 wt %, about 210 wt %, about 215 wt %, about 220 wt %,about 225 wt %, about 230 wt %, or greater of the liquid medium (e.g.,water), based on the combined solids weight of the urea-modifiedaldehyde-based resin and the isocyanate-based resin. For example, thebinder, prior to curing, can include one or more liquid mediums (e.g.,water) in an amount of about 145 wt % to about to about 225 wt %, about150 wt % to about 215 wt %, about 155 wt % to about 205 wt %, about 160wt % to about 210 wt %, about 160 wt % to about 185 wt %, about 160 wt %to about 170 wt %, about 170 wt % to about 185 wt %, or about 165 wt %to about 175 wt %, based on the combined solids weight of theurea-modified aldehyde-based resin and the isocyanate-based resin.

As used herein, the term “extender” refers to materials that can beadded to the binder that occupy volume and also contribute to bondingproperties of the binder. One example of a suitable extender can be amaterial that includes one or more proteins. The protein can contributeto the crosslinking of the mixture during at least partial cure thereof.Suitable extenders can be or include, but are not limited to, one ormore flours, spray dried blood, or any mixture thereof. Illustrativeflours can be or include, but are not limited to, wheat flour, cornflour, soy flour, oat flour, other grain flours, nut or seed flour(e.g., almond, walnut, pecan, cashew, or peanut), millet flour, brandsthereof, starches thereof, or any mixture thereof. In some embodiments,the extender can be or include corn flours or corn starches, such asNCS-83, NCS-74, and 4501 flours, commercially available from DidionMilling Company, Inc., Sun Prairie, Wis. In other embodiments, theextender can be or include wheat flours, wheat starches, and/or wheatderived protein-starch composition, such as Glu-X extender, commerciallyavailable from Siemer Milling Company, Teutopolis, Ill. Illustrativepolysaccharides can include, but are not limited to, starch, cellulose,gums, such as guar and xanthan, alginates, pectin, gellan, or anymixture thereof. Suitable polysaccharide starches can include, forexample maize or corn, native corn starch (NCS), waxy maize, highamylose maize, potato, tapioca, wheat starch, or any mixture thereof.Other starches, such as genetically engineered starches, can be orinclude high amylose potato starches, potato amylopectin starches, orany mixture thereof. In one or more embodiments, the extender can be orinclude one, two, or more grain flours. For example, the extender can beor include one or more corn flours, one or more wheat flours, acombination thereof, or a mixture thereof.

Illustrative soy flour can be or can include a raw soy protein and/or asoy protein modified as discussed and described in U.S. Pat. No.6,497,760. Raw soy protein maybe in the form of ground whole beans(including the hulls, oil, protein, minerals, or other components), ameal (extracted or partially extracted), a flour (generally containingless than 1.5 wt % of oil and about 30 wt % to about 35 wt % ofcarbohydrate), or an isolate (a substantially pure protein flourcontaining less than 0.5% oil and less than 5% carbohydrate). Suitablesoy protein can be derived from any source of soy protein such assoybean concentrate or soybean meal. Protein-rich soybean-derivedflours, such as soy protein isolate, protein concentrate, and ordinarydefatted soy flour, which contain about 20 wt % to about 95 wt % ofprotein, can also be used. The source of soy protein (soy flour) can besubstantially free of functional urease. Information on soy protein canbe found in, for example, Kirk-Othmer, Encyclopedia of ChemicalTechnology, Fourth Edition, Volume 22, pp. 591-619 (1997). Modified soyprotein can be modified with either of two classes of modifiers. Thefirst class of modifiers can include saturated and unsaturated C₈-C₂₂sulfates and sulfonates, such as alkali metal salts. Illustrativemodifiers in the first class can be or include, but are not limited to,sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, salts thereof,hydrates thereof, or any mixture thereof. The second class of modifiersincludes compounds having the chemical formula R₂NC(═X)NR₂, where each Rgroup can independently be a hydrogen, a C₁-C₄ saturated hydrocarbylgroup, or an C₂-C₄ unsaturated hydrocarbyl group; and X can be O, NH, orS. The C₁-C₄ saturated hydrocarbyl groups refer to alkyl groups (bothstraight and branched chain) and the C₂-C₄ unsaturated hydrocarbylgroups refer to alkenyl and alkynyl groups (both straight and branchedchain). Illustrative modifiers in the second class can be or include,but are not limited to, urea, guanidine (e.g., guanidine hydrochloride),salts thereof, hydrates thereof, or any mixture thereof. Other suitablemodifiers and/or extenders can include, but are not limited to, thosediscussed and described in U.S. Pat. Nos. 2,507,465; 2,492,510;2,781,286; 3,285,805; 3,957,703; 4,070,314; 4,244,846; and 4,778,530.

In some embodiments, the binder can include the extender in an amount ofabout 0.1 wt %, about 0.5 wt %, about 1 wt %, about 2 wt %, about 3 wt%, or about 5 wt % to about 6 wt %, about 8 wt %, about 10 wt %, about12 wt %, or about 15 wt %, based on the total weight of the binder. Thebinder can include about 8 wt %, about 10 wt %, about 15 wt %, about 20wt %, about 25 wt %, about 30 wt %, or about 35 wt % to about 40 wt %,about 45 wt %, about 50 wt %, about 55 wt %, about 57 wt %, about 62 wt%, or greater of the extender, based on the combined solids weight ofthe urea-modified aldehyde-based resin and the isocyanate-based resin.In some embodiments, the binder can include one or more extenders in anamount of about 10 wt % to about 62 wt %, 11 wt % to about 20 wt %,about 13.9 wt % to about 50.6 wt %, about 17 wt % to about 33 wt %,about 23 wt % to about 40 wt %, about 26 wt % to about 42 wt %, about 31wt % to about 48 wt %, about 46 wt % to about 58 wt %, or about 52 wt %to about 62 wt %, based on the combined solids weight of theurea-modified aldehyde-based resin and the isocyanate-based resin. Inanother embodiment, the binder can include at least 10 wt %, at least 12wt %, at least 14 wt %, at least 16 wt %, at least 18 wt %, at least 20wt %, at least 22 wt %, or at least 24 wt % to about 30 wt %, about 35wt %, about 40 wt %, about 45 wt %, about 50 wt %, about 55 wt %, about57 wt %, or about 62 wt %, based on the combined solids weight of theurea-modified aldehyde-based resin and the isocyanate-based resin. Inanother embodiment, the binder can include about 8 wt %, about 10 wt %,about 12 wt %, about 14 wt %, about 16 wt %, about 18 wt %, or about 20wt % to less than 26 wt %, less than 30 wt %, less than 35 wt %, lessthan 40 wt %, less than 45 wt %, less than 50 wt %, less than 55 wt %,or less than 60 wt %, based on the combined solids weight of theurea-modified aldehyde-based resin and the isocyanate-based resin.

In some embodiments, the binder can also include one or more fillers. Asused herein, the term “filler” refers to materials that can be added tothe binder that occupy volume but do not contribute or do notsubstantially contribute to bonding properties of the binder. Generally,both extenders and fillers occupy volume of the binder, but extendersfurther contribute to bonding properties of the binder. Any extender canbe used as a filler to occupy volume, but a filler used as an extenderdoes not substantially contribute to bonding properties of the binder.

Suitable fillers can be or include, but are not limited to, nutshellmedia, corn media or corn cob media, furfural residues, seed shellmedia, fruit pit media, animal bones, milwhite, clays, glasses,inorganic oxides such as silica and/or alumina, wood flour, ground bark,e.g., alder bark, or any mixture thereof. Nutshell media can be orinclude whole, broken, chopped, crushed, milled, and/or ground shellsfrom one or more nuts and/or seeds. Illustrative nutshell media caninclude, but is not limited to, almond shells, walnut shells, pecanshells, chestnut shells, hickory nut shells, cashew nut shells, peanutshells, macadamia nut shells, ivory nut shells, brazil nut shells, pinenut shells, filbert nut (hazel nut) shells, soy nut shells, pistachionut shells, coconut shells, or the like, or any mixture thereof.

Corn media can be or include broken, chopped, crushed, or ground corncobs, corn stalks, or other corn derived products, or any mixturethereof. Corn media can also include furfural residue from corn cobs,corn stalks, or other corn derived products and can be referred to as“corn cobs” or “corn cob residue”. An illustrative corn derived productcan include, but is not limited to, a cellulose byproduct derived fromthe manufacture of furfural, such as WILVACO-FIL® corn cob residue,commercially available from Willamette Valley Company, Inc., Eugene,Oreg. Furfural residues, including floral and furfural-derivedcompounds, can also come from oat, wheat, wheat bran, barely, woodparticles, sawdust, and/or other plant-based products.

Illustrative seed shells (including fruit pits), can include, but arenot limited to, the seed shells of fruit, e.g., plum, peach, cherry,apricot, olive, mango, jackfruit, guava, custard apples, pomegranates,pumpkins, and watermelon, ground or crushed seed shells of other plantssuch as maize (e.g., corn cobs or corn kernels), wheat, rice, jowar,sunflowers, or the like, or any mixture thereof. Other examples ofsuitable fillers include, but are not limited to, wheat shell, cornhusk, olive pit, peanut shell, or any combination thereof. In at leastone embodiment, the nut shells and/or seed shells may be ground orpowdered, e.g., in a flour form. Suitable flours derived from nuts ornut shells may include, but are not limited to, walnut shell flour,pecan shell flour, almond shell flour, hazelnut shell flour, or anymixture thereof. In other embodiments, a fruit pit flour, i.e., a flourderived from the pits or seed shells of fruits can be or include, but isnot limited to, olive pit flour, apricot pit flour, peach pit flour,prune pit flour, or any mixture thereof. In one or more embodiments, thefiller can be or include one or more nutshell flours, one or more fruitpit flours, or a mixture thereof. For example, the filler can be orinclude walnut shell flour, olive pit flour, a combination thereof, or amixture thereof.

If the binder includes the filler, the binder can include about 0.1 wt%, about 0.3 wt %, about 0.5 wt %, about 0.7 wt %, about 1 wt %, about1.5 wt %, about 2 wt %, about 2.5 wt %, or about 3 wt % to about 5 wt %,about 6 wt %, about 7 wt %, about 8 wt %, about 9 wt %, about 10 wt %,about 11 wt %, about 12 wt %, about 13 wt %, about 14 wt %, or about 15wt % of the filler, based on the total weight of the binder. If thebinder includes the filler, the binder can include about 1 wt %, about 4wt %, about 6 wt %, about 8 wt %, about 9 wt %, about 10 wt %, or about12 wt % to about 14 wt %, about 16 wt %, about 18 wt %, about 20 wt %,about 25 wt %, about 30 wt %, about 40 wt %, about 45 wt %, about 50 wt%, about 55 wt %, about 60 wt %, about 62 wt %, or greater of thefiller, based on the combined solids weight of the urea-modifiedaldehyde-based resin and the isocyanate-based resin. In someembodiments, the binder can include one or more fillers in an amount ofabout 5 wt % to about 50 wt %, about 8 wt % to about 31 wt %, about 6.5wt % to about 30 wt %, about 8 wt % to about 62 wt %, about 10 wt % toabout 26 wt %, about 7 wt % to about 20 wt %, about 12 wt % to about 30wt %, about 8 wt % to about 18 wt %, about 8.2 wt % to about 36.3 wt %,about 18 wt % to about 25 wt %, or about 10.5 wt % to about 18.2 wt %,based on the combined solids weight of the urea-modified aldehyde-basedresin and the isocyanate-based resin. In another embodiment, the bindercan include at least 6 wt %, at least 8 wt %, at least 10 wt %, or atleast 12 wt % to 14 wt %, 16 wt %, 18 wt %, about 21 wt %, about 25 wt%, about 30 wt %, about 35 wt %, about 40 wt %, or about 45 wt % of thefiller, based on the combined solids weight of the urea-modifiedaldehyde-based resin and the isocyanate-based resin. In anotherembodiment, the binder can include about 5 wt %, about 7 wt %, about 9wt %, or about 11 wt % to less than 20 wt %, less than 25 wt %, lessthan 30 wt %, less than 35 wt %, less than 40 wt %, or less than 45 wt%, based on the combined solids weight of the urea-modifiedaldehyde-based resin and the isocyanate-based resin.

In one or more embodiments, the binder can include the extender and thefiller. In some embodiments, the extender can be or include, but is notlimited to, wheat flour, corn flour, or a mixture thereof and the fillercan be or include, but is not limited to, walnut shell flour, olive pitflour, corn cob residue, or a mixture thereof.

The fillers and/or extenders can have an average particle size of about0.1 μm to about 100 μm. For example, the average particle size of thefillers and/or extenders can be about 1 μm, about 3 μm, about 5 μm,about 8 μm, or about 10 μm to about 30 μm, about 40 μm, about 50 μm, orabout 60 μm. In another example, the average particle size of thefillers and/or extenders can be about 7 μm to about 30 μm, about 10 μmto about 30 μm, about 20 μm to about 35 μm, about 0.1 μm to about 10 μm,about 5 μm to about 45 μm, about 15 μm to about 35 μm, or about 10 μm toabout 50 μm.

The average particle size and the maximum particle size of the fillerand/or extender can be measured with a Cilas 990D Particle Size Analyzerconfigured with Particle Expert software. A vacuum cleaner equipped witha HEPA filter or equivalent capable of capturing the sample to bemeasured can be used. It should be ensured that the feeder mechanism,venturi block, and lenses are completely clean. Calibration should beunnecessary unless the detector or laser has been repaired or replaced.If calibration is required, the procedure can use Whitehouse CertifiedGlass Beads or other material meeting the requirements of ISO13320:2009.

In some embodiments, if the binder includes both the extender and thefiller, the amount of the extender can be about 0.1 wt % to about 99.9wt %, based on a combined weight of the extender and the filler. Inanother embodiment, if the binder includes both the extender and thefiller, the amount of the extender can be about 0.1 wt %, about 0.5 wt%, about 1 wt %, about 5 wt %, about 10 wt %, about 15 wt %, or about 20wt % to about 30 wt %, about 40 wt %, about 50 wt %, about 60 wt %,about 70 wt %, about 80 wt %, about 85 wt %, about 90 wt %, about 95 wt%, about 99 wt %, about 99.5 wt %, or about 99.9 wt %, based on thecombined weight of the extender and the filler. In some embodiments, thebinder can include a greater amount of filler than extender. In otherembodiments, the binder can include a greater amount of extender thanfiller.

In some embodiments, the binder can also include one or moresurfactants. The surfactant can be or include one or more nonionicsurfactants, one or more anionic surfactants, one or more cationicsurfactants, or any mixture thereof. Illustrative nonionic surfactantscan be or include, but are not limited to, one or more acetylenic diolcompounds and/or ethylene glycol, such as SURFYNOL® 104E nonionicsurfactant, wetting agent, and molecular defoamer, commerciallyavailable from Air Products, Inc., polyethylene glycol (PEG) includingPLURACOL® polyols, PEG-4, PEG-6, PRG-8, PEG-12, PEG-75, and PEG-150, allcommercially available from BASF, Co.; polyoxyethylene glycol alkylethers, octaethylene glycol monododecyl ether, pentaethylene glycolmonododecyl ether, polyoxypropylene glycol alkyl ethers, polyoxyethyleneglycol octylphenol ethers (TRITON® X-100), polyoxyethylene glycolalkylphenol ethers (nonoxynol-9), or any mixture thereof. Anionicsurfactants can have anionic functional groups at the chain head, suchas carboxylates, phosphate, sulfate, sulfonate, and other anionicgroups. Illustrative anionic surfactants can be or include, but are notlimited to, one or more lignosulfonates, alkyl sulfates (e.g., laurylsulfates), alkyl-ether sulfates, or any mixture thereof. Exemplarylignosulfonates can include, but are not limited to, sodiumlignosulfonate, lithium lignosulfonate, potassium lignosulfonate,calcium lignosulfonate, magnesium lignosulfonate, ammoniumlignosulfonate, alkylammonium lignosulfonate, salts thereof, complexesthereof, or any mixture thereof. Illustrative cationic surfactants canbe or include, but are not limited to, one or more quaternary ammoniumcations, such as, alkyltrimethylammonium salts: cetyl trimethylammoniumbromide (CTAB), cetyl trimethylammonium chloride (CTAC), cetylpyridiniumchloride (CPC), benzalkonium chloride (BAC), benzethonium chloride(BZT), 5-bromo-5-nitro-1,3-dioxane, dimethyldioctadecylammoniumchloride, cetrimonium bromide, dioctadecyldimethylammonium bromide(DODAB), salts thereof, complexes thereof, or any mixture thereof.

In some embodiments, the binder can include the surfactant in an amountof about 0.01 wt %, about 0.05 wt %, about 0.07 wt %, about 0.1 wt %,about 0.13 wt %, or about 0.15 wt % to about 0.2 wt %, about 0.25 wt %,about 0.3 wt %, about 0.35 wt %, about 0.4 wt %, about 0.45 wt %, orabout 0.5 wt %, based on the total weight of the binder. In otherembodiments, the binder can include the surfactant in an amount of about0.01 wt %, about 0.02 wt %, about 0.03 wt %, about 0.04 wt %, about 0.05wt %, about 0.07 wt %, about 0.09 wt %, about 0.1 wt %, about 0.11 wt %,about 0.12 wt %, or about 0.13 wt % to about 0.14 wt %, about 0.15 wt %,about 0.16 wt %, about 0.17 wt %, or about 0.18 wt % to about 0.19 wt %,about 0.2 wt %, about 0.25 wt %, about 0.3 wt %, about 0.35 wt %, about0.4 wt %, about 0.45 wt %, about 0.5 wt %, about 0.6 wt %, about 0.7 wt%, about 0.8 wt %, about 0.9 wt %, about 1 wt %, about 2 wt %, about 3wt %, or greater, based on the combined solids weight of theurea-modified aldehyde-based resin and the isocyanate-based resin. Inother embodiments, the binder can include about 0.001 wt % to about 3 wt%, about 0.01 wt % to about 3 wt %, about 0.05 wt % to about 3 wt %,about 0.1 wt % to about 3 wt %, about 0.001 wt % to about 2 wt %, about0.01 wt % to about 2 wt %, about 0.05 wt % to about 2 wt %, about 0.1 wt% to about 2 wt %, about 0.001 wt % to about 1 wt %, about 0.01 wt % toabout 1 wt %, about 0.05 wt % to about 1 wt %, about 0.1 wt % to about 1wt %, about 0.001 wt % to about 0.5 wt %, about 0.01 wt % to about 0.5wt %, about 0.05 wt % to about 0.5 wt %, or about 0.1 wt % to about 0.5wt % of the surfactant, based on the combined solids weight of theurea-modified aldehyde-based resin and the isocyanate-based resin.

In some embodiments, the binder can also include one or more salts. Thesalt can have one or more cations and one or more anions. Illustrativecations can be or include, but are not limited to, sodium, potassium,lithium, cesium, calcium, magnesium, barium, copper, cobalt, zinc,manganese, aluminum, ammonium, alkylammonium, complexes thereof,hydrates thereof, or any mixture thereof. Illustrative anions can be orinclude, but are not limited to, carbonates, bicarbonates, halides(e.g., chlorides or bromides), hydroxides, nitrates, nitrites,silicates, acetates, citrates, formates, sulfates, phosphates, or anymixture thereof. In some specific embodiments, the salt can be orinclude one or more carbonates, such as, sodium carbonate (e.g., sodaash), potassium carbonate, calcium carbonate; one or more hydroxides,such as, sodium hydroxide, potassium hydroxide, lithium hydroxide,ammonium hydroxide; salts thereof; hydrates thereof; or any mixturethereof. In some embodiments, the hydroxide can be or include sodiumhydroxide and the carbonate can be or include sodium carbonate. In someembodiments, the salt can be or can include, but is not limited to,sodium chloride, potassium chloride, calcium chloride, sodium carbonate,potassium carbonate, calcium carbonate, sodium sulfate, potassiumsulfate, calcium sulfate, magnesium sulfate, or any mixture thereof.

In some embodiments, the binder can include the salt, e.g., a carbonateand/or a hydroxide, in an amount of about 0.05 wt %, about 0.1 wt %,about 0.5 wt %, or about 1 wt % to about 2 wt %, about 3 wt %, about 4wt %, about 5 wt %, about 6 wt %, about 7 wt %, about 8 wt % or about 9wt %, based on the total weight of the binder. It should be understoodthat the hydroxides, e.g., sodium hydroxide, and the carbonates, e.g.,sodium carbonate, are each encompassed by the term “base compound” andthe term “salt”. In some embodiments, the binder can include a combinedor total amount of any base compound(s) and any salt(s) of up to about 3wt %, about 4 wt %, about 5 wt %, about 5.5 wt %, about 6 wt %, about6.5 wt %, about 7 wt %, about 7.5 wt %, about 8 wt %, about 8.5 wt %, orabout 9 wt %, based on the total weight of the binder.

In some embodiments, the binder can include the salt, e.g., a carbonateand/or a hydroxide, in an amount of about 0.1 wt %, about 1 wt %, about3 wt %, about 5 wt %, about 6 wt %, about 7 wt %, or about 8 wt % toabout 9 wt %, about 10 wt %, about 12 wt %, about 15 wt %, about 17 wt%, about 20 wt %, about 22 wt %, about 24 wt %, about 26 wt %, or about27 wt %, based on the combined solids weight of the urea-modifiedaldehyde-based resin and the isocyanate-based resin. In someembodiments, the binder can include the salt, e.g., a carbonate and/or ahydroxide, in an amount of about 0.05 wt %, about 0.1 wt %, about 0.2 wt%, about 0.3 wt %, about 0.4 wt %, about 0.5 wt %, about 0.6 wt %, about0.7 wt %, or about 0.8 wt % to about 0.9 wt %, about 1 wt %, about 1.2wt %, about 1.5 wt %, about 2 wt %, about 2.5 wt %, about 3 wt %, about3.5 wt %, about 4 wt %, about 4.5 wt %, about 5 wt %, about 6 wt %,about 7 wt %, about 8 wt %, about 9 wt %, about 10 wt %, or greater,based on the combined solids weight of the urea-modified aldehyde-basedresin and the isocyanate-based resin. In other embodiments, the bindercan include the salt in an amount of about 0.05 wt % to about 5 wt %,about 0.1 wt % to about 5 wt %, about 0.1 wt % to about 4 wt %, about0.1 wt % to about 3 wt %, about 0.1 wt % to about 2.5 wt %, about 0.1 wt% to about 2 wt %, about 0.1 wt % to about 1.5 wt %, about 0.1 wt % toabout 1 wt %, about 0.1 wt % to about 0.5 wt %, about 0.2 wt % to about5 wt %, about 0.2 wt % to about 4 wt %, about 0.2 wt % to about 3 wt %,about 0.2 wt % to about 2.5 wt %, about 0.2 wt % to about 2 wt %, about0.2 wt % to about 1.5 wt %, about 0.2 wt % to about 1 wt %, about 0.2 wt% to about 0.5 wt %, about 0.5 wt % to about 5 wt %, about 0.5 wt % toabout 4 wt %, about 0.5 wt % to about 3 wt %, about 0.5 wt % to about2.5 wt %, about 0.5 wt % to about 2 wt %, about 0.5 wt % to about 1.5 wt%, about 0.5 wt % to about 1 wt %, about 0.8 wt % to about 5 wt %, about0.8 wt % to about 4 wt %, about 0.8 wt % to about 3 wt %, about 0.8 wt %to about 2.5 wt %, about 0.8 wt % to about 2 wt %, about 0.8 wt % toabout 1.5 wt %, or about 0.8 wt % to about 1 wt %, based on the combinedsolids weight of the urea-modified aldehyde-based resin and theisocyanate-based resin.

In some embodiments, the binder, prior to curing, can include ahydroxide in an amount of about 1 wt % to about 20 wt % and a carbonatein an amount of about 0.1 wt % to about 8 wt %, based on the combinedsolids weight of the urea-modified aldehyde-based resin and theisocyanate-based resin. In other embodiments, the binder, prior tocuring, can include a hydroxide in an amount of about 2 wt % to about 19wt % and a carbonate in an amount of about 0.1 wt % to about 7 wt %,based on the combined solids weight of the urea-modified aldehyde-basedresin and the isocyanate-based resin. In other embodiments, the binder,prior to curing, can include a hydroxide in an amount of about 3 wt % toabout 18 wt % and a carbonate in an amount of about 0.1 wt % to about 6wt %, based on the combined solids weight of the urea-modifiedaldehyde-based resin and the isocyanate-based resin. In otherembodiments, the binder, prior to curing, can include a hydroxide in anamount of about 3.5 wt % to about 17 wt % and a carbonate in an amountof about 0.1 wt % to about 5 wt %, based on the combined solids weightof the urea-modified aldehyde-based resin and the isocyanate-basedresin.

As noted above, the hydroxides, e.g., sodium hydroxide, and thecarbonates, e.g., sodium carbonate, are each a base compound and a salt.In some embodiments, the binder can include about 3 wt %, about 3.5 wt%, about 4 wt %, or about 4.5 wt % to about 5 wt %, about 5.5 wt %,about 6 wt %, about 6.5 wt %, about 7 wt %, about 7.5 wt %, about 8 wt%, about 8.5 wt %, or about 9 wt % of a total amount of any basecompound(s) and any salt(s), based on a total weight of the binder. Insome embodiments, the binder can include up to 5.8 wt %, up to 6.8 wt %,or up to 7.8 wt % of one or more hydroxides, e.g., sodium hydroxide, andup to 2.3 wt %, up to 2.5 wt %, or up to 2.7 wt % of one or morecarbonates, such that the binder can include up to 3.9 wt %, up to 4.1wt %, up to 8.1 wt %, up to 9.3 wt %, or up to 10.5 wt % of a combinedamount of the one or more hydroxides and the one or more carbonates.

In some embodiments, the binder can also include one or more additives.Illustrative additives can include, but are not limited to, waxes and/orother hydrophobic additives, release agents, dyes, fire retardants,formaldehyde scavengers, biocides, or any mixture thereof. In someembodiments, the mixtures, compositions, and products, including, butnot limited to, the binder, mixtures that include the binder, resins,and/or lignocellulose substrates, can be produced by agitating, mixing,blending, homogenization, ultrasonication, colloid milling, microfluidicmixing, or processes.

The rate at which the crosslinking reactions occur during curing of thebinder can affect what is commonly referred to as the binder “pot life”,“shelf life”, or “gel time”. The terms “pot life”, “shelf life”, and“gel time” usually refers to the time required for the binder to cure,which can be measured a number of ways, but near the end of the pot lifethe viscosity of the binder is too high for satisfactory application ofthe binder to a substrate, such as the lignocellulose substrates.

The binder can be formed by combining together, e.g., mixing, blending,or otherwise contacting, the individual components while maintaining aflowable condition, such as having a relatively low viscosity (e.g.,about 10,000 cP or less, about 9,000 cP or less, about 8,000 cP or less,about 7,000 cP or less, about 6,000 cP or less, about 5,000 cP or less,about 4,000 cP or less, or about 3,500 cP or less at a temperature ofabout 25° C.), prior to spreading, spraying, coating, or otherwiseapplying the binder onto the lignocellulose substrates. In this way, thebinder can have a pot life long enough for performing commercial bondingapplications. Depending on the particular use or application for thebinder, the viscosity of the binder can increase to a point at which thebinder can no longer be efficiently or effectively applied to thelignocellulose substrates, e.g., a plurality of wood particles, a woodcomposite, and/or veneer substrate. The usable pot life of the binderhas been exceeded once the viscosity of the binder increases to a pointthat causes the binder to be too thick or viscous to apply or otherwiseuse. The binder can have pot life of at least 6 hours, at least 12hours, at least 18 hours, at least 1 day, about 2 days, about 3 days,about 5 days, about 7 days, or about 10 days to about 12 days, about 14days, about 18 days, about 22 days, about 25 days, about 28 days, about30 days, or longer, after formation of the binder. After formation ofthe binder is the period of time starting when the binder is initiallymixed, produced, or otherwise formed. The binder can be maintained at atemperature of about 10° C. to about 40° C. or about 20° C. to about 30°C., such as about 25° C., during the period of time. The binder can becontinuously or intermittently stirred when in storage to reduce orprevent phase separation of the binder. The binder can have a solidscontent of about 40 wt %, about 41 wt %, about 42 wt %, about 43 wt %,or about 44 wt % to about 45 wt %, about 46 wt %, about 47 wt %, about48 wt %, about 49 wt %, or about 50 wt %. In at least one embodiment,the binder can have a solids content of about 42 wt %, about 43 wt %, orabout 44 wt % to about 45 wt %, about 46 wt %, about 47 wt %, or about48 wt %, based on the total weight of the binder.

In one or more embodiments, the binder, prior to being cured, can have aviscosity of about 100 cP, about 200 cP, about 300 cP, about 400 cP,about 500 cP, about 600 cP, about 700 cP, about 800 cP, about 900 cP,about 1,000 cP, about 1,100 cP, about 1,200 cP, about 1,300 cP, or about1,400 cP to about 1,500 cP, about 1,800 cP, about 2,000 cP, about 2,200cP, about 2,500 cP, about 2,800 cP, about 3,000 cP, about 3,200 cP,about 3,500 cP, about 4,000 cP, about 6,000 cP, about 8,000 cP, about10,000 cP, or greater at a temperature of about 25° C. In someembodiments, the binder, prior to being cured, can have a viscosity ofabout 500 cP to about 10,000 cP, about 100 cP to about 3,000 cP, about100 cP to about 2,500 cP, about 100 cP to about 2,000 cP, about 100 cPto about 1,500 cP, about 100 cP to about 1,000 cP, about 100 cP to about900 cP, about 100 cP to about 800 cP, about 200 cP to about 3,000 cP,about 200 cP to about 2,500 cP, about 200 cP to about 2,000 cP, about200 cP to about 1,500 cP, about 200 cP to about 1,200 cP, about 200 cPto about 1,000 cP, about 200 cP to about 900 cP, about 200 cP to about800 cP, about 200 cP to about 3,000 cP, about 400 cP to about 2,500 cP,about 400 cP to about 2,000 cP, about 400 cP to about 1,500 cP, about400 cP to about 1,200 cP, about 400 cP to about 1,000 cP, about 400 cPto about 900 cP, about 400 cP to about 800 cP, about 500 cP to about3,000 cP, about 500 cP to about 2,500 cP, about 500 cP to about 2,000cP, about 500 cP to about 1,500 cP, about 500 cP to about 1,200 cP,about 500 cP to about 1,000 cP, about 500 cP to about 900 cP, about 500cP to about 800 cP, about 500 cP to about 700 cP, about 500 cP to about600 cP, about 500 cP to about 550 cP, about 600 cP to about 3,000 cP,about 600 cP to about 2,500 cP, about 600 cP to about 2,000 cP, about600 cP to about 1,500 cP, about 600 cP to about 1,000 cP, about 600 cPto about 800 cP, about 600 cP to about 700 cP, or about 600 cP to about650 cP at a temperature of about 25° C.

The viscosity of the compositions, e.g., the binder, discussed anddescribed herein can be determined using a viscometer at a temperatureof about 25° C. For example, a Model DV-II+ viscometer, commerciallyavailable from Brookfield Company, Inc., equipped with a number 3spindle can be used to measure viscosity. The binder can be maintainedat a temperature of about 25° C.

In one or more embodiments, the binder can have an initial viscosity ofless than 10,000 cP, less than 9,000 cP, less than 8,000 cP, less than7,000 cP, less than 6,000 cP, less than 5,000 cP, less than 4,000 cP, orless than 3,500 cP at a temperature of about 25° for at least the first12 hours after formation of the binder. In some embodiments, the bindercan have an initial viscosity of about 50 cP, about 100 cP, about 200cP, about 400 cP, about 500 cP, about 800 cP, about 1,000 cP, about1,200 cP, or about 1,500 cP to about 1,600 cP, about 1,800 cP, about2,000 cP, about 2,200 cP, about 2,500 cP, about 2,800 cP, about 3,000cP, about 3,200 cP, about 3,500 cP, 5,000 cP, about 7,000 cP, about8,000 cP, or about 10,000 cP at a temperature of about 25° C. for about6 hours, about 12 hours, about 18 hours, about 24 hours, about 36 hours,about 2 days, about 3 days, about 5 days, or about 8 days to about 10days, about 12 days, about 14 days, about 18 days, about 22 days, about25 days, about 28 days, about 30 days, or longer, after formation of thebinder. In other embodiments, the binder can have an initial viscosityof 500 cP to about 10,000 cP, about 80 cP to about 3,400 cP, about 80 cPto about 3,100 cP, about 80 cP to about 2,900 cP, about 200 cP to about3,500 cP, about 200 cP to about 3,100 cP, about 200 cP to about 2,900cP, about 400 cP to about 3,500 cP, about 400 cP to about 3,100 cP, orabout 400 cP to about 2,900 cP at a temperature of about 25° C. forabout 6 hours, about 12 hours, about 24 hours, about 2 days, about 5days, or about 8 days to about 10 days, about 15 days, about 20 days,about 25 days, about 30 days, or longer, after formation of the binder.

In other embodiments, the binder can have an initial viscosity of about50 cP, about 100 cP, about 200 cP, about 400 cP, about 600 cP, about 800cP, about 1,000 cP, about 1,200 cP, or about 1,500 cP to less than 2,000cP, less than 2,200 cP, less than 2,500 cP, less than 2,800 cP, lessthan 3,000 cP, less than 3,200 cP, less than 3,500 cP, less than 4,000cP, less than 6,000 cP, less than 8,000 cP, or less than 10,000 cP at atemperature of about 25° C. for at least the first 6 hours, at least thefirst 12 hours, at least 1 day, at least 2 days, at least 3 days, atleast 5 days, or at least 8 days to about 10 days, about 12 days, about14 days, about 18 days, about 22 days, about 25 days, about 28 days,about 30 days, or longer, after formation of the binder. In someembodiments, the binder can have an initial viscosity of about 900 cP toless than 10,000 cP, about 80 cP to less than 3,500 cP, about 80 cP toless than 3,100 cP, about 80 cP to less than 2,900 cP, about 200 cP toless than 3,500 cP, about 200 cP to less than 3,300 cP, about 200 cP toless than 3,100 cP, about 200 cP to less than 3,000 cP, about 400 cP toless than 3,500 cP, about 400 cP to less than 3,300 cP, about 400 cP toless than 3,100 cP, or about 400 cP to less than 3,000 cP at atemperature of about 25° C. for at least the first 6 hours, at least thefirst 12 hours, at least 1 day, at least 2 days, at least 5 days, or atleast 8 days to about 10 days, about 15 days, about 20 days, about 25days, or about 30 days, after formation of the binder.

In one or more embodiments, the binder, prior to being cured, can have aviscosity of about 100 cP, about 200 cP, about 300 cP, about 400 cP,about 500 cP, about 600 cP, about 700 cP to about 800 cP, about 900 cP,about 1,000 cP, about 1,100 cP, about 1,200 cP, about 1,500 cP, about1,800 cP, about 2,000 cP, about 2,200 cP, about 2,500 cP, about 2,800cP, about 3,000 cP, about 3,200 cP, about 3,500 cP, about 4,000 cP,about 6,000 cP, about 8,000 cP, or about 10,000 cP at a temperature ofabout 25° C. and a solids content of about 43 wt % to about 46 wt % orabout 44 wt % to about 45 wt %. In some embodiments, the binder, priorto being cured, can have a viscosity of about 900 cP to about 10,000 cP,about 1,000 cP to about 9,000 cP, about 1,000 cP to about 3,500 cP,about 100 cP to about 3,000 cP, about 100 cP to about 2,500 cP, about100 cP to about 2,000 cP, about 100 cP to about 1,500 cP, about 100 cPto about 1,000 cP, about 100 cP to about 900 cP, about 100 cP to about800 cP, about 200 cP to about 3,000 cP, about 200 cP to about 2,500 cP,about 200 cP to about 2,000 cP, about 200 cP to about 1,500 cP, about200 cP to about 1,200 cP, about 200 cP to about 1,000 cP, about 200 cPto about 900 cP, about 200 cP to about 800 cP, about 200 cP to about3,000 cP, about 400 cP to about 2,500 cP, about 400 cP to about 2,000cP, about 400 cP to about 1,500 cP, about 400 cP to about 1,200 cP,about 400 cP to about 1,000 cP, about 400 cP to about 900 cP, about 400cP to about 800 cP, about 500 cP to about 3,000 cP, about 500 cP toabout 2,500 cP, about 500 cP to about 2,000 cP, about 500 cP to about1,500 cP, about 500 cP to about 1,200 cP, about 500 cP to about 1,000cP, about 500 cP to about 900 cP, about 500 cP to about 800 cP, about500 cP to about 700 cP, about 500 cP to about 600 cP, about 500 cP toabout 550 cP, about 600 cP to about 3,000 cP, about 600 cP to about2,500 cP, about 600 cP to about 2,000 cP, about 600 cP to about 1,500cP, about 600 cP to about 1,000 cP, about 600 cP to about 800 cP, about600 cP to about 700 cP, or about 600 cP to about 650 cP at a temperatureof about 25° C. and a solids content of about 43 wt % to about 46 wt %or about 44 wt % to about 45 wt %.

In one or more embodiments, the binder, prior to being cured, can havean initial viscosity of less 10,000 cP, less than 8,000 cP, less than6,000 cP, less than 4,000 cP, or than 3,500 cP at a temperature of about25° C. and a solids content of about 43 wt % to about 45 wt % for atleast the first 12 hours after formation of the binder. In someembodiments, the binder can have an initial viscosity of about 50 cP,about 100 cP, about 200 cP, about 400 cP, about 500 cP, about 800 cP,about 1,000 cP, about 1,200 cP, or about 1,500 cP to about 1,600 cP,about 1,800 cP, about 2,000 cP, about 2,200 cP, about 2,500 cP, about2,800 cP, about 3,000 cP, about 3,200 cP, about 3,500 cP, about 4,000cP, about 5,000 cP, about 6,000 cP, about 7,000 cP, about 8,000 cP, orabout 9,000 cP at a temperature of about 25° C. and a solids content ofabout 43 wt % to about 45 wt % for about 6 hours, about 12 hours, about18 hours, about 24 hours, about 36 hours, about 2 days, about 3 days,about 5 days, or about 8 days to about 10 days, about 12 days, about 14days, about 18 days, about 22 days, about 25 days, about 28 days, about30 days, or longer, after formation of the binder. In other embodiments,the binder, prior to curing, can have an initial viscosity at about 80cP to about 3,400 cP, about 80 cP to about 3,100 cP, about 80 cP toabout 2,900 cP, about 200 cP to about 3,500 cP, about 200 cP to about3,100 cP, about 200 cP to about 2,900 cP, about 400 cP to about 3,500cP, about 400 cP to about 3,100 cP, or about 400 cP to about 2,900 cP ata temperature of about 25° C. and a solids content of about 43 wt % toabout 45 wt % for about 6 hours, about 12 hours, about 24 hours, about 2days, about 5 days, or about 8 days to about 10 days, about 15 days,about 20 days, about 25 days, about 30 days, or longer, after formationof the binder.

In other embodiments, the binder can have an initial viscosity of about50 cP, about 100 cP, about 200 cP, about 400 cP, about 600 cP, about 800cP, about 1,000 cP, about 1,200 cP, or about 1,500 cP to less than 2,000cP, less than 2,200 cP, less than 2,500 cP, less than 2,800 cP, lessthan 3,000 cP, less than 3,200 cP, less than 3,500 cP, less than 4,000cP, less than 6,000 cP, less than 8,000 cP, or less than 10,000 cP at atemperature of about 25° C. and a solids content of about 43 wt % toabout 45 wt % for at least the first 6 hours, at least the first 12hours, at least 1 day, at least 2 days, at least 3 days, at least 5days, or at least 8 days to about 10 days, about 12 days, about 14 days,about 18 days, about 22 days, about 25 days, about 28 days, about 30days, or longer, after formation of the binder. In some embodiments, thebinder can have an initial viscosity at about 80 cP to less than 3,500cP, about 80 cP to less than 3,100 cP, about 80 cP to less than 2,900cP, about 200 cP to less than 3,500 cP, about 200 cP to less than 3,300cP, about 200 cP to less than 3,100 cP, about 200 cP to less than 3,000cP, about 400 cP to less than 3,500 cP, about 400 cP to less than 3,300cP, about 400 cP to less than 3,100 cP, or about 400 cP to less than3,000 cP at a temperature of about 25° C. and a solids content of about43 wt % to about 45 wt % for at least the first 6 hours, at least thefirst 12 hours, at least 1 day, at least 2 days, at least 5 days, or atleast 8 days to about 10 days, about 15 days, about 20 days, about 25days, or about 30 days, after formation of the binder.

The binder, prior to curing, can have a pH of greater than 7. In someembodiments, the binder, prior to curing, can have a pH of about 7.5,about 8.0, about 9.0, about 9.5, about 10.0, about 10.5, or about 11.0to about 11.2, about 11.5, about 11.7, about 12.0, about 12.2, about12.5, or about 13.0 at a temperature of about 25° C. In anotherembodiment, the binder, prior to curing, can have a pH of about 8 toabout 13, about 9 to about 13, about 10 to about 13, about 11 to about13, about 12 to about 13, about 9 to about 12.5, about 10 to about 12.5,about 11 to about 12.5, about 12 to about 12.5, about 9 to about 12,about 10 to about 12, about 11 to about 12, about 11.5 to about 12,about 11.2 to about 12.5, about 11.5 to about 12.5, or about 11.7 toabout 12.5 at a temperature of about 25° C. In one or more embodiments,prior to curing, the binder can have a pH of about 10.5 to about 13.0 ata temperature of about 25° C.

In some embodiments, the binder, prior to curing, can have a pH of about7.5, about 8.0, about 9.0, about 9.5, about 10.0, about 10.5, or about11.0 to about 11.2, about 11.5, about 11.7, about 12.0, about 12.2,about 12.5, or about 13.0 at a temperature of about 25° C. and a solidscontent of about 43 wt % to about 46 wt % or about 44 wt % to about 45wt %. In another embodiment, the binder, prior to curing, can have a pHof about 8 to about 13, about 9 to about 13, about 10 to about 13, about11 to about 13, about 12 to about 13, about 9 to about 12.5, about 10 toabout 12.5, about 11 to about 12.5, about 12 to about 12.5, about 9 toabout 12, about 10 to about 12, about 11 to about 12, about 11.5 toabout 12, about 11.2 to about 12.5, about 11.5 to about 12.5, or about11.7 to about 12.5 at a temperature of about 25° C. and a solids contentof about 43 wt % to about 45 wt %. In one or more embodiments, prior tocuring, the binder can have a pH of about 10.5 to about 13.0 at atemperature of about 25° C. and a solids content of about 43 wt % toabout 46 wt % or about 44 wt % to about 45 wt %.

In some embodiments, the binder, prior to curing, can have a sodiumhydroxide equivalent weight alkalinity of about 3 wt %, about 4 wt %,about 5 wt %, about 5.3 wt %, about 5.5 wt %, about 5.7 wt %, or about 6wt % to about 6.3 wt %, about 6.5 wt %, about 6.7 wt %, about 7 wt %,about 7.3 wt %, about 7.5 wt %, about 8 wt %, about 8.5 wt %, or about 9wt %. In some embodiments, the binder, prior to curing, can have asodium hydroxide equivalent weight alkalinity of about 3 wt %, about 4wt %, about 5 wt %, about 5.3 wt %, about 5.5 wt %, about 5.7 wt %, orabout 6 wt % to about 6.3 wt %, about 6.5 wt %, about 6.7 wt %, about 7wt %, about 7.3 wt %, or about 7.5 wt %, about 8 wt %, about 8.5 wt %,or about 9 wt % at a temperature of about 25° C. In some embodiments,the binder, prior to curing, can have a sodium hydroxide equivalentweight alkalinity of about 3 wt %, about 4 wt %, about 5 wt %, about 5.3wt %, about 5.5 wt %, about 5.7 wt %, or about 6 wt % to about 6.3 wt %,about 6.5 wt %, about 6.7 wt %, about 7 wt %, about 7.3 wt %, or about7.5 wt %, about 8 wt %, about 8.5 wt %, or about 9 wt % at a temperatureof about 25° C. and a solids content of about 43 wt % to about 46 wt %or about 44 wt % to about 45 wt %.

In some embodiments, prior to curing, the binder can be free offormaldehyde, i.e., the binder can have no detectable free formaldehydeconcentration. In other embodiments, prior to curing, the binder canhave a free formaldehyde concentration of about 1 ppm, about 10 ppm,about 100 ppm, about 200 ppm, about 500 ppm, or about 700 ppm to about800 ppm, about 900 ppm, about 0.1 wt %, about 0.15 wt %, about 0.2 wt %,about 0.25 wt %, about 0.3 wt %, or about 0.4 wt %, based on the basedon the combined solids weight of the urea-modified aldehyde-based resinand the isocyanate-based resin. In other embodiments, prior to curing,the binder can have a free formaldehyde concentration of less than 1ppm, less than 10 ppm, less than 100 ppm, less than 200 ppm, less than500 ppm, less than 700 ppm, less than 800 ppm, less than 900 ppm, lessthan 0.1 wt %, less than 0.15 wt %, less than 0.2 wt %, less than 0.25wt %, less than 0.3 wt %, or less than 0.4 wt %, based on the based onthe combined solids weight of the urea-modified aldehyde-based resin andthe isocyanate-based resin.

As used herein, the term “lignocellulose” refers to a material thatincludes lignin and cellulose, hemicellulose, or a combination ofcellulose and hemicelluloses. The starting material, from which thelignocellulose substrates can be or can be derived from, can be shaped,reduced, or otherwise formed to the appropriate dimensions by variousprocesses such as hogging, grinding, hammer milling, tearing, shredding,and/or flaking. Other processes for producing the substrates can includeskiving, cutting, slicing, and/or sawing. Suitable forms of thelignocellulose substrates can include, but are not limited to, chips,flakes, wafers, fibers, powder, shavings, sawdust or dust, veneer,strands, and/or the like. Accordingly, the term “substrate” when used inconjunction with “lignocellulose” refers to lignocellulose material orlignocellulose containing material having any desired shape such aschips, flakes, fibers, powder, shavings, sawdust or dust, veneer,strands, and/or the like. Other suitable lignocellulose substrates caninclude, but are not limited to, wood chips, wood fibers, wood flakes,wood strands, wood wafers, wood shavings, wood particles, wood veneer,or any mixture thereof.

Lignocellulose substrates can be or include, but are not limited to, oneor more hardwoods, one or more softwoods, a mixture of hardwood andsoftwood, other plant materials, or any combination thereof. Thelignocellulose substrates (material that includes both cellulose andlignin) can include, but is not limited to, straw, hemp, sisal, cottonstalk, wheat, bamboo, sabai grass, rice straw, banana leaves, papermulberry (i.e., bast fiber), abaca leaves, pineapple leaves, espartograss leaves, fibers from the genus Hesperaloe in the family Agavaceaejute, salt water reeds, palm fronds, flax, ground nut shells, hardwoods,softwoods, recycled fiberboards such as high density fiberboard, mediumdensity fiberboard, low density fiberboard, oriented strand board,particleboard, animal fibers (e.g., wool, hair), recycled paper products(e.g., newspapers, cardboard, cereal boxes, and magazines), or anycombination thereof. Suitable woods can include softwoods and/orhardwoods. Illustrative types of wood can include, but are not limitedto, one or more of: alder, almond, apple, ash, aspen, basswood, beech,birch, cedar, cherry, chinaberry, cottonwood, cypress, douglas fir, elm,fir, gum, hackberry, helm, hickory, huiache, jessamine, lenga, maple,oak, olive, pear, pecan, pine, poplar, redwood, sassafras, spruce,sycamore, tallow, tepa, walnut, and willow.

The lignocellulose substrates can include or contain water on, about,and/or within the substrates. In some embodiments, the lignocellulosesubstrates can have a moisture or water content of about 9 wt %, about10 wt %, about 11 wt %, about 12 wt %, or about 13 wt % to about 14 wt%, about 15 wt %, about 16 wt %, about 17 wt %, about 18 wt %, about 19wt %, about 20 wt %, about 25 wt %, about 30 wt %, about 35 wt %, about40 wt %, or greater, based on the dry weight of the lignocellulosesubstrates. In other embodiments, the lignocellulose substrates can havewater content of about 9 wt % to about 40 wt %, about 10 wt % to about40 wt %, about 10 wt % to about 35 wt %, about 10 wt % to about 30 wt %,about 10 wt % to about 25 wt %, about 10 wt % to about 20 wt %, about 10wt % to about 18 wt %, about 10 wt % to about 16 wt %, about 10 wt % toabout 15 wt %, about 10 wt % to about 14 wt %, about 10 wt % to about 13wt %, about 10 wt % to about 12 wt %, about 10 wt % to about 11 wt %,about 12 wt % to about 40 wt %, about 12 wt % to about 35 wt %, about 12wt % to about 30 wt %, about 12 wt % to about 25 wt %, about 12 wt % toabout 20 wt %, about 12 wt % to about 18 wt %, about 12 wt % to about 16wt %, about 12 wt % to about 15 wt %, about 12 wt % to about 14 wt %,about 12 wt % to about 13 wt %, about 14 wt % to about 40 wt %, about 14wt % to about 35 wt %, about 14 wt % to about 30 wt %, about 14 wt % toabout 25 wt %, about 14 wt % to about 20 wt %, about 14 wt % to about 18wt %, about 14 wt % to about 16 wt %, or about 14 wt % to about 15 wt %,based on the dry weight of the lignocellulose substrate. In anotherembodiment, the lignocellulose substrates can have water content of atleast 9 wt %, at least 10 wt %, at least 11 wt %, at least 12 wt %, atleast 13 wt %, at least 14 wt %, at least 15 wt %, at least 16 wt %, atleast 17 wt %, at least 18 wt %, at least 19 wt %, or at least 20 wt %to about 21 wt %, about 23 wt %, about 25 wt %, about 27 wt %, about 30wt %, about 33 wt %, about 35 wt %, about 37 wt %, about 40 wt %, orgreater, based on the dry weight of the lignocellulose substrates.

The lignocellulose substrates can be fresh, e.g., not treated or dried,or dried and/or treated. In some embodiments, the lignocellulosesubstrates and/or the starting material from which the lignocellulosesubstrates were derived can be at least partially dried. As such, insome embodiments, the lignocellulose substrates can have a moisture orwater content of less than 9 wt %, less than 8 wt %, less than 7 wt %,e.g., from about 3 wt % to about 7 wt %, based on the dry weight of thelignocellulose substrates. In other embodiments, the lignocellulosesubstrates can be washed and/or leached with an aqueous medium such aswater.

In one or more embodiments, the binder composition can be mixed,blended, sprayed, applied, or otherwise contacted with thelignocellulose substrates to produce a mixture or resinated furnish. Theresinated furnish can be heated in air. The resinated furnish can beheated in an inert atmosphere or a substantially an inert atmospheresuch as nitrogen. If the mixture is heated in a substantially inertatmosphere, the amount of oxygen can be less than 5 mol %, less than 3mol %, less than 1 mol %, less than 0.5 mol %, or less than 0.1 mol %oxygen relative to the balance of gases in the inert atmosphere.Suitable inert gases can include, but are not limited to, nitrogen,argon, helium, or a mixture thereof.

Heating the binder and/or the resinated furnish can cause or promote theat least partial curing of the binder to produce the composite product.As used herein, the terms “curing,” “cured,” “at least partiallycuring,” “at least partially cured,” and similar terms are intended torefer to the structural and/or morphological change that occurs in themixture, such as by covalent chemical reaction (crosslinking), ionicinteraction or clustering, phase transformation or inversion, and/orhydrogen bonding when the is subjected to conditions sufficient, e.g.,sufficiently heated, to cause the properties of a flexible, poroussubstrate, such as a nonwoven mat or blanket of lignocellulosesubstrates and/or a rigid or semi-rigid substrate, such as a wood orother lignocellulose containing board or sheet, to which an effectiveamount of the binder has been applied, to be altered. The lignocellulosesubstrates can have the moisture content (e.g., about or at least 10 wt% to about 40 wt % or more, based on the dry weight of thelignocellulose substrates), at the time the binder is at least partiallycured (e.g., heated to a temperature of about 60° C. to about 300° C.)to produce the composite lignocellulose product.

Illustrative composite products can be or include, but are not limitedto, plywood (e.g., hardwood plywood and/or softwood plywood), orientedstrand board (“OSB”), engineered wood flooring, particleboard,fiberboard (e.g., medium density fiberboard (“MDF”) and/or high densityfiberboard (“HDF”)), chipboard, flakeboard, or waferboard, structuralcomposite lumber, glue-laminated lumber (Glulam) other wood and non-woodproducts. Structural composite lumber can include, but is not limitedto, laminated veneer lumber (LVL), parallel strand lumber (PSL),laminated strand lumber (LSL), and oriented strand lumber (OSL).

The lignocellulose substrates can be arranged, positioned, stacked,combined, mixed, or otherwise disposed within a resinated furnishcontaining one or more binders or adhesives in an uncured configurationof the desired composite product or wood-based product. For example, aplurality of lignocellulose substrates, such as multiple wood veneersand/or wood sheets, can be arranged with a binder therebetween toproduce a resinated furnish having an uncured configuration of plywood,LVL, PSL, LSL, OSL, Glulam, or other engineered composite product. Inother examples, the plurality of lignocellulose substrates can bestrands, chips, flakes, and/or particles that can be arranged with abinder therebetween to produce a resinated furnish having an uncuredconfiguration of OSB, LVL, PSL, LSL, OSL, particleboard, fiberboard,MDF, HDF, chipboard, flakeboard, or waferboard.

Composite products such as particleboard, fiberboard, plywood, andoriented strand board, can have a thickness of about 1.5 mm, about 5 mm,or about 10 mm to about 15 mm, about 20 mm, about 25 mm, about 30 mm,about 50 mm, about 100 mm, about 200 mm, or about 300 mm. The compositeproducts can have a length of about 0.1 m, about 0.5 m, about 1 m, about1.2 m, about 1.5 m, about 1.8 m, about 2.4 m, about 3 m, or about 3.6 m.The composite products can have a width of about 0.1 m, about 0.5 m,about 1 m, about 1.2 m, about 1.5 m, about 1.8 m, about 2.4 m, or about3 m.

In some embodiments, the composite product can include one or moreveneers or other wood sheets. For example, a composite product caninclude two, three, four, five, six, seven, eight, nine, ten, or moreveneers or other wood sheets. The veneers or wood sheets can have anysuitable shape, e.g., rectangular, circular, or any other geometricalshape. Typically, the veneers can be rectangular and can have a widthranging from a low of about 1 cm, about 5 cm, about 10 cm, about 15 cm,about 20 cm, or about 25 cm to a high of about 0.6 m, about 0.9 m, about1.2 m, about 1.8 m, or about 2.4 m. The veneers can have a lengthranging from a low of about 0.3 m, about 0.6 m, about 0.9 m, about 1.2m, or about 1.8 m to a high of about 2.4 m, or about 3 m, about 3.6 m,about 4.3 m, about 4.9 m, about 5.5 m, about 6.1 m, about 6.7 m, about7.3 m, or about 7.9 m. For example, in a typical veneer product such asplywood, the veneers can have a width of about 1.2 m and a length ofabout 2.4 m. The veneers can have a thickness ranging from a low ofabout 0.8 mm, about 0.9 mm, about 1 mm, about 1.1 mm or about 1.2 mm toa high of about 3 mm, about 4 mm, about 5 mm, about 6 mm, about 7 mm,about 8 mm, about 9 mm, or about 10 mm.

Composite products in the shape or form of a panel, sheet, board,veneer, or the like can be in the form of a rectangular prism thatincludes six outer surfaces, e.g., three pairs of oppositely facingsurfaces. The first pair of oppositely facing surfaces of the compositeproduct can include a first or “top” surface and an opposing second or“bottom” surface. The second and third pairs of oppositely facingsurfaces of the composite product can be referred to as the “sidesurfaces” that have a surface area less than the surface area of thefirst and second surfaces. As such, composite products in the shape orform of a panel, sheet, board, or the like can have an averagethickness, where the average thickness is the length or distance betweenthe first and second surfaces.

If the composite product is in the form of a panel, sheet, board, or thelike, the amount or length of time the resinated furnish can be heatedcan be about 5 seconds per millimeter (s/mm), about 10 s/mm, about 12s/mm, or about 15 s/mm to about 17 s/mm, about 19 s/mm, about 21 s/mm,about 23 s/mm, about 25 s/mm, about 27 s/mm, about 30 s/mm, about 35s/mm, about 40 s/mm, about 50 s/mm, or about 60 s/mm, where the lengthrefers to the average thickness of the composite product. For example,the resinated furnish can be heated for a time of about 5 s/mm to about55 s/mm, about 10 s/mm to about 45 s/mm, about 15 s/mm to about 40 s/mm,about 5 s/mm to about 25 s/mm, about 7 s/mm to about 27 s/mm, about 9s/mm to about 24 s/mm, about 11 s/mm to about 22 s/mm, about 8 s/mm toabout 20 s/mm, about 14 s/mm to about 18 s/mm, about 6 s/mm to about 14s/mm, about 10 s/mm to about 18 s/mm, or about 10 s/mm to about 16 s/mm,where the length refers to the average thickness of the compositeproduct. In another embodiment, the resinated furnish can be heated fora time less than 120 s/mm, less than 110 s/mm, less than 100 s/mm, lessthan 90 s/mm, less than 80 s/mm, less than 70 s/mm, less than 60 s/mm,less than 50 s/mm, less than 40 s/mm, less than 30 s/mm, less than 25s/mm, less than 22 s/mm, less than 20 s/mm, less than 18 s/mm, less than17 s/mm, less than 16 s/mm, less than 15 s/mm, less than 14 s/mm, lessthan 13 s/mm, or less than 12 s/mm, where the length refers to theaverage thickness of the composite product. In one specific embodiment,a composite product in the form of a panel, sheet, board, or the likeand having an average thickness of about 15 mm and subjected to a totalheating time of about 4 minutes would correspond to heating the mixturefor about 16 s/mm. In at least one specific embodiment, the resinatedfurnish can be heated to a temperature of about 100° C. to about 300°C., about 100° C. to about 250° C., about 100° C. to about 200° C.,about 100° C. to about 170° C., about 140° C. to about 170° C., or about160° C. to about 170° C. for a time of about 10 s/mm to about 30 s/mm,about 13 s/mm to about 19 s/mm, about 15 s/mm to about 40 s/mm, or about8 s/mm to about 50 s/mm.

Pressure can optionally be applied to the resinated furnish before,during, and/or after the resinated furnish is heated to produce thecomposite product. For example, if the desired composite product shapeor structure is a panel, sheet, board, or the like, an amount of theresinated furnish sufficient to produce a composite product of thedesired size, can be transported, directed, placed, introduced,disposed, or otherwise located within a press capable of pressing themixture before the mixture is heated and/or when the mixture is heated.The press can be an open press or a closed press. In at least onespecific embodiment, an open press can be used to press the resinatedfurnish when the resinated furnish is heated, e.g., to a temperature ofabout 100° C. to about 300° C. or about 100° C. to about 250° C. Inanother embodiment, the resinated furnish can be extruded through a die(extrusion process) and heated to produce the composite lignocelluloseproduct. The resinated furnish can be pressed under a pressure of about0.5 MPa, about 1 MPa, about 3 MPa, or about 5 MPa to about 7 MPa, about9 MPa, about 11 MPa, about 13 MPa, about 15 MPa, or about 20 MPa. In oneembodiment, the resinated furnish can be heated to a temperature of atleast 100° C. to about 160° C. and can be pressed to a pressure of about0.8 MPa to about 2 MPa for about 2 min to about 20 min to produce thecomposite product. In some embodiments, the resinated furnish can beheated to a temperature of about 100° C. to about 160° C., about 120° C.to about 160° C., or about 140° C. to about 160° C. and can be pressedto a pressure of about 1 MPa to about 2 MPa or about 1.5 MPa to about 2MPa for about 2 min, about 3 min, about 5 min, or about 8 min to about10 min, about 15 min, about 18 min, or about 20 min to produce thecomposite product.

Illustrative open presses can be as discussed and described in U.S. Pat.Nos. 4,017,248; 5,337,655; 5,611,269; 5,950,532; 6,098,532; and6,782,810. Suitable, commercially available, open presses can include,but are not limited to, the CONTIROLL® press available from Siempelkamp,GmbH and the CPS press available from Dieffenbacher, GmbH.

The resinated furnish can be made via a continuous process or asemi-continuous mixing process in one or more mixers, blenders, or otheragitators. The mixer can be configured to contain a few hundredkilograms to several thousand kilograms. For example, in a single mixerabout 500 kg/hr, about 5,000 kg/hr, about 10,000 kg/hr, or about 13,000kg/hr to about 16,000 kg/hr, about 20,000 kg/hr, about 25,000 kg/hr, orabout 30,000 kg/hr of the mixture can be recovered from the mixer. Asthe binder or the resinated furnish exits the mixer, the composition ormixture can be deposited onto a conveyor belt and can be transported toone or more dryers, moistening systems, presses, and/or other processingequipment. For example, in at least one specific embodiments, aparticleboard product can be made by blending, mixing, or otherwisecombining a first or “face” mixture in a first mixer and a second or“core” mixture in a second mixer. The first mixer can produce about13,600 kg/hr to about 15,900 kg/hr of a “face” mixture and the secondmixer can produce about 18,100 kg/hr to about 20,400 kg/hr of a “core”mixture. The “face” and “core” mixtures can be used to produce aparticleboard panel or sheet, where the “face” mixture makes up theouter layers of the particleboard and the “core” mixture makes up theinner or core layer of the particleboard.

The composite product can have physical-mechanic properties, such asinternal bond (IB) strength, blending, density, and/or moisture content,according to EN 13986, EN 314, EN 310, EN 323, and/or EN 322. Thecomposite product can have a Wood Failure according to PS1-09.

Referring to particleboard in particular, particleboard made accordingto one or more embodiments described herein can meet or exceed therequirements for H-1, H-2, H-3, M-0, M-1, M-S, M-2, M-3i, LD-1, and/orLD-2 grade particleboard as described in the American National StandardsInstitute (ANSI) for particleboard, i.e., ANSI A208.1-2009Particleboard, approved Feb. 2, 2009. Particleboard made according toone or more embodiments described herein can meet or exceed therequirements for PBU, D-2, D-3, and/or M-3 as defined by the ANSI forparticleboard, i.e., ANSI A208.1-2009 Particleboard, approved Feb. 2,2009. For example, Tables A and B set out certain requirements for thedifferent grades of particleboard. Referring to oriented strand board(OSB) in particular, OSB made according to one or more embodimentsdescribed herein can meet or exceed the U.S. Department of CommerceVoluntary Performance Standard PS 2. Referring to plywood in particular,plywood made according to one or more embodiments described herein canmeet or exceed the U.S. Department of Commerce Voluntary ProductStandard PS 1-09 (May 2007) and/or PS 2-10 (June 2011).

Internal bond strength of the composite product can be measured bypulling the composite apart in a direction perpendicular to the planeformed by the test piece. The internal bond strength and/or the waterabsorption of the finished product can be measured according to ASTMD1037-96a. Swell due to water absorption can be measured by measuringthe thickness of the finished product before and after the waterabsorption test. The temperature of the lignocellulose substrates can bemeasured using any type of thermocouple or other temperature sensingdevice. For example, the temperature of the lignocellulose substratescan be measured using an infrared temperature sensor.

In one embodiment, the manufacture of a composite product can includecombining a core, a first outer layer, a second outer layer, and abinder to produce a mixture and heating the mixture to produce acomposite lignocellulose product. The mixture can include the binderdisposed on at least a portion of each of the core, the first outerlayer, and the second outer layer. For example, the binder can bedisposed between the first outer layer and the first side of the coreand between the second outer layer and the second side of the core. Thecomposite product can include the at least partially cured binder, thefirst outer layer bonded to a first side of the core by the binder andthe second outer layer bonded to a second side of the core by the atleast partially cured binder. The first side and the second side of thecore oppose one another. Each of the core, the first outer layer, andthe second outer layer can independently include a lignocellulosesubstrate (e.g., veneer or wood sheet) or material having a watercontent of about 10 wt % to about 40 wt %, based on a dried weight ofthe lignocellulose substrates. Each of the first binder and the secondbinder, prior to curing, can independently include: a urea-modifiedaldehyde-based resin in an amount of about 90 wt % to about 99.5 wt %and an isocyanate-based resin in an amount of about 0.5 wt % to about 10wt %, based on a combined solids weight of the urea-modifiedaldehyde-based resin and the isocyanate-based resin.

In some embodiments, the composite product can include the plurality oflignocellulose substrates and one or more binders disposed on at least aportion of each lignocellulose substrate. The lignocellulose substratescan have a water content of about 10 wt % to about 40 wt %, based on adried weight of the lignocellulose substrates. In some embodiments, thebinder can include about 30 wt % to about 40 wt % of solids that caninclude the urea-modified aldehyde-based resin, about 0.1 wt % to about3 wt % of the isocyanate-based resin, about 0.1 wt % to about 12 wt % ofthe extender, and about 50 wt % to about 62 wt % of water, where allweight percent values are based on a total weight of the binder. Inother embodiments, the binder can include the urea-modifiedaldehyde-based resin in an amount of about 90 wt % to about 99.5 wt %,the isocyanate-based resin in an amount of about 0.5 wt % to about 10 wt%, the extender in an amount of about 3 wt % to about 20 wt %, and waterin an amount of about 145 wt % to about 230 wt %, based on a combinedsolids weight of the urea-modified aldehyde-based resin and theisocyanate-based resin. The binder can have a pH of about 10.5 to about13.0 and can have a viscosity of about 200 cP to about 10,000 cP, about500 cP to about 9,000 cP, about 1,000 to about 8,700 cP, about 1,100 cPto about 7,000 cP, about 1,200 cP to about 6,600 cP, about 1,000 cP toabout 3,500 cP, about 900 cP to about 3,000 cP, about 800 cP to about2,000 cP, or about 700 cP to about 1,500 cP at a temperature of about25° C. upon formation of the binder.

In one or more embodiments, the composite products made with the bindercan be structural products. The structural products can be formed bybonding a plurality of lignocellulose substrates together with thebinder to provide a structural product for use as a structural member orsupport in the construction of floors, walls, roofs, and otherstructural components. As such, the binder or composite products madetherewith can satisfy any one or more of the following standardizedtests: ASTM D2559-12a(2018), Standard Specification for Adhesives forbonded Structural Wood Products for Use under Exterior ExposureConditions; ASTM D3737-18e1, Standard Practice for EstablishingAllowable Properties for Structural Glued Laminated Timber (Glulam);ASTM D5456-19, Standard Specification for Evaluation of StructuralComposite Lumber Products; ASTM D5764-97a(2018), Standard Test Methodfor Evaluating Dowel-Bearing Strength of Wood and Wood-based Products;ASTM D6815-09(2015), Standard Specification for Evaluation of Durationof Load and Creep Effects of Wood and Wood-Based Products; ASTM D7247-17Standard Test Method for Evaluating the Shear Strength of Adhesive Bondsin Laminated Wood Products of Elevated temperatures; ASTMD3535-07a(2013) Standard Test Method for Resistance to creep UnderStatic Loading for Structural Wood Laminating Adhesives Used UnderExterior Exposure Conditions; CSA 0112.9 (2014) Evaluation of Adhesivesfor Structural Wood Products (Exterior Exposure); and/or CSA0112.10-2008 (R2017) Evaluation of Adhesives for Structural WoodProducts (Limited Moisture Exposure). In some embodiments, the compositelignocellulose product can be a structural composite lumber. Thestructural composite lumber can be laminated veneer lumber, parallelstrand lumber, and/or laminated strand lumber.

EXAMPLES

In order to provide a better understanding of the foregoing discussion,the following non-limiting examples are offered. Although the examplesmay be directed to specific examples, they are not to be viewed aslimiting the invention in any specific respect. All parts, proportions,and percentages are by weight unless otherwise indicated.

In Examples (Exs.) 1-50 and Comparative Examples (CExs.) 1-11, thephenol-formaldehyde resin was GPR 5815 resin, commercially availablefrom Georgia-Pacific Chemicals LLC in South America. Thephenol-formaldehyde resin had a formaldehyde to phenol molar ratio ofabout 2.35:1, a solids content of about 42 wt % to about 45 wt % (e.g.,about 43.5 wt %), a pH of about 11 to about 12, and a viscosity of about350 cP to about 800 cP at a temperature of about 25° C., a density ofabout 1.175 g/cm³ to about 1.195 g/cm³, a free formaldehyde content ofabout 0.3% or less, a gel time of about 10 minutes to about 18 minutes,and an alkalinity of about 5.5 to about 6.5. The surfactant was thenonionic wetting agent and molecular defoamer SURFYNOL® 104E,commercially available from Air Products, Inc. The surfactant containedethylene glycol and 2,4,7,9-tetramethyl-5-decyne-4,7-diol. Thesurfactant was a clear to pale yellow liquid, had an activity of about50%, a viscosity of about 100 mPa·s at a temperature of about 20° C., aspecific gravity of about 1 at a temperature of about 21° C., a flashpoint of about 111° C., and a pour point of about −17° C. The pMDI wasDESMODUR® 44V20L resin, commercially available from Covestro. The pMDIwas a liquid, dark brown polymeric isocyanate based on 4,4′-methylenediphenyl diisocyanate with isomers and homologues of higherfunctionality. The pMDI had an NCO content of about 30.5 wt % to about32.5 wt %, a viscosity of about 160 cP to about 240 cP at a temperatureof about 25° C., a density of about 1.23 g/cm³, a maximumphenylisocyanate content of 50 ppm, and a specific heat of about 1.51kJ/kgK.

The viscosity of the binders made in Exs 1-50 and CEx 1-11 weredetermined at a temperature of about 25° C. using a Model DV-II+viscometer, commercially available from Brookfield Company, Inc., with anumber 3 spindle. The binders made in Exs 1-50 and CEx 1-11 weremaintained in a water bath at a temperature of about 25° C., during the30 days after formation of the respective binder. The binders wereperiodically stirred when stored to reduce or prevent phase separationof the respective binder.

Examples 1-10—Binder Compositions

For Exs. 1-10, each binder was prepared according to the followingprocedure. To a blend tank equipped with an agitator, about 143 g ofwater and about 670 g of phenol-formaldehyde resin were added. Theagitator was started. To the blend tank, in the following order and timeframe: about 77 g of total extender (wheat flour and/or corn flour perrespective example, as listed in Table 1) was added over about 2 min toabout 5 min; about 2 g of soda ash was added over about 0.1 min to about1 min; about 55 g of total filler (olive pit flour and/or walnut shellflour per respective example, as listed in Table 1) was added over about2 min to about 5 min; about 1 g of the surfactant was added over about0.1 min to about 1 min; and about 32 g of aqueous sodium hydroxidesolution (about 50 wt % of solid sodium hydroxide and about 50 wt % ofwater) was added over about 2 min to about 4 min. The components of thebinder were mixed at a temperature of about 15° C. to about 40° C. Themixture was agitated for about 2 min to about 3 min, then agitation wasstopped. To the mixture, about 10 g of pMDI was added over about 1 minto about 3 min. The agitator was started. To the mixture, about 10 g ofwater was added over about 1 min to about 5 min, then agitation wasstopped, and the mixture, i.e., the binder composition, was dischargedinto a container.

The binder composition of Exs. 1-10 contained about 96.7 wt % ofphenol-formaldehyde resin solids, about 3.3 wt % of pMDI solids, about25.5 wt % of total extender, about 18.2 wt % of total filler, and about181.6 wt % of water, based on a combined solids weight of thephenol-formaldehyde resin and the pMDI. As such, the binder compositionshad a solids content of about 44.2 wt % and a water content of about55.8 wt %, based on the total weight of the binder. The binders of Exs.1-10 all had a pH of about 11.5 to about 12.3 at a temperature of about25° C.

TABLE 1 Binder Compositions for Examples 1-10 Extenders Fillers WheatFlour Corn Flour Olive Pit Flour Walnut Shell Flour Ex. (wt %)¹ (wt %)¹(wt %)² (wt %)² 1 100 0 0 100 2 75 25 0 100 3 50 50 0 100 4 25 75 0 1005 0 100 0 100 6 100 0 100 0 7 75 25 100 0 8 50 50 100 0 9 25 75 100 0 100 100 100 0 ¹wt % based on the combined weight of the corn and wheatflours ²wt % based on the combined weight of the olive pit and walnutshell flours

Examples 1-10—Binder Viscosities

For the binders of Exs. 1-10, the viscosity was measured and recorded ata temperature of 25° C. on the referenced days for each respectiveexample, as listed in Table 2, starting immediately after the binder wasformed (Day 1). Accordingly, the viscosity values on Day 2 were measured24 hours after the binder was formed, the viscosity values on Day 3 weremeasured 48 hours after the binder was formed, and so on with eachsubsequent day adding another 24 hours of time.

TABLE 2 Binder Viscosities (cP) for Examples 1-10 Days Ex. 1 2 4 8 9 1011 12 15 1 1093 2130 2580 2660 3020 3047 3233 3467 3740 2 745 1450 15971737 1913 2013 2117 2173 2457 3 600 1050 1192 1337 1457 1457 1567 15531850 4 441 693 723 846 874 865 950 976 1155 5 330 416 450 502 588 586582 604 687 6 638 1423 1727 1787 — 1930 — — 2020 7 621 1145 1240 1417 —1440 — — 1523 8 444 716 781 886 — 911 — — 1027 9 369 518 533 577 — 632 —— 680 10 286 348 339 375 — 401 — — 407 Days Ex. 16 17 19 22 23 26 30 13760 3967 4037 — — — — 2 2420 2500 2630 2800 2927 3193 3360 3 1937 19201907 2020 2163 2420 2780 4 1197 1190 1250 1360 1377 1587 1867 5 692 738760 800  845 905 969 6 — 2013 2087 2162 — 2242 2404 7 — 1523 1567 1605 —1662 1800 8 — 987 1075 1101 — 1141 1278 9 — 697 731 761 — 795 875 10 —407 449 460 — 481 568

Surprisingly and unexpectedly, the binders of Exs. 1-10 all maintained aviscosity of less than 3,500 cP at a temperature of about 25° C. for atleast 12 days after formation of the binders.

Examples 11-20—Binder Compositions

For Exs. 12-20, each binder was prepared according to the followingprocedure. To a blend tank equipped with an agitator, about 134 g ofwater and about 670 g of phenol-formaldehyde resin were added. Theagitator was started. To the mixture, in the following order and timeframe: about 71 g of total extenders (wheat flour and/or corn flour perrespective example, as listed in Table 3) was added over about 2 min toabout 5 min; about 2 g of soda ash was added over about 0.1 min to about1 min; about 50 g of total fillers (olive pit flour and/or walnut shellflour per respective example, as listed in Table 3) was added over about2 min to about 5 min; about 1 g of surfactant was added over about 0.1min to about 1 min; and about 32 g of aqueous sodium hydroxide solution(about 50 wt % of solid sodium hydroxide and about 50 wt % of water) wasadded over about 2 min to about 4 min. The components of the binder weremixed at a temperature of about 15° C. to about 40° C. The mixture wasagitated for about 2 min to about 3 min, then agitation was stopped. Tothe mixture, about 20 g of pMDI was added over about 1 min to about 3min. The agitator was started. To the mixture, about 20 g of water wasadded over about 1 min to about 5 min, then agitation was stopped, andthe mixture, i.e., the binder composition, was discharged into acontainer.

The binder composition of Exs. 11-20 contained about 93.6 wt % ofphenol-formaldehyde resin solids, about 6.4 wt % of pMDI solids, about22.8 wt % of total extender, about 16.1 wt % of total filler, and about176.1 wt % of water, based on a combined solids weight of thephenol-formaldehyde resin and the pMDI. As such, the binder compositionshad a solids content of about 44.1 wt % and a water content of about55.9 wt %, based on the total weight of the binder. The binders of Exs.11-20 all had a pH of about 11.5 to about 12.3 at a temperature of about25° C.

TABLE 3 Binder Compositions for Examples 11-20 Extenders Fillers WheatFlour Corn Flour Olive Pit Flour Walnut Shell Flour Ex. (wt %)¹ (wt %)¹(wt %)² (wt %)² 11 100 0 0 100 12 75 25 0 100 13 50 50 0 100 14 25 75 0100 15 0 100 0 100 16 100 0 100 0 17 75 25 100 0 18 50 50 100 0 19 25 75100 0 20 0 100 100 0 ¹wt % based on the combined weight of the corn andwheat flours ²wt % based on the combined weight of the olive pit andwalnut shell flours

Examples 11-20—Binder Viscosities

For the binders of Exs. 11-20, the viscosity was measured and recordedat a temperature of 25° C. on the referenced days for each respectiveexample, as listed in Table 4, starting immediately after the binder wasformed (Day 1). Accordingly, the viscosity values on Day 2 were measured24 hours after the binder was formed, the viscosity values on Day 3 weremeasured 48 hours after the binder was formed, and so on with eachsubsequent day adding another 24 hours of time.

TABLE 4 Binder Viscosities (cP) for Examples 11-20 Days Ex. 1 2 3 4 7 89 10 11 14 15 11 1340 — 2773 — 3220 3393 3400 3813 4053 — — 12 1275 —2560 — 3060 3427 3540 3767 3920 4100 — 13 703 — 1220 — 1443 1533 15401667 1697 1950 2110 14 510 — 768 — 885 905 940 1080 1123 1300 1390 15351 — 458 — 517 593 617 672 685  828 844 16 740 1477 — 1753 — 1907 —2043 — — 2230 17 621 1208 — 1423 — 1500 — 1717 — — 1827 18 412 716 — 863— 916 — 966 — — 1017 19 337 508 — 544 — 608 — 642 — — 701 20 263 322 —329 — 362 — 383 — — 411 Days Ex. 16 17 18 19 21 22 25 26 29 30 11 — — —— — — — — — — 12 — — — — — — — — — — 13 2183 — 2290 — 2597 2887 3393 —3787 — 14 1447 — 1593 — 1770 1870 2300 — 2523 — 15  835 —  928 — 10351103 1190 — 1485 — 16 — 2200 — 2353 — 2408 — 2490 — 2602 17 — 1830 —1850 — 1890 — 1925 — 1946 18 — 1043 — 1097 — 1111 — 1136 — 1190 19 — 713— 770 — 832 — 841 — 867 20 — 421 — 438 — 449 — 490 — 504

Surprisingly and unexpectedly, the binders of Exs. 11-20 all maintaineda viscosity of less than 3,500 cP at a temperature of about 25° C. forat least 8 days after formation of the binders.

Examples 21-30—Binder Compositions

For Exs. 21-30, each binder was prepared according to the followingprocedure. To a blend tank equipped with an agitator, about 125 g ofwater and about 670 g of phenol-formaldehyde resin were added. Theagitator was started. To the mixture, in the following order and timeframe: about 64 g of total extenders (wheat flour and/or corn flour perrespective example, as listed in Table 5) was added over about 2 min toabout 5 min; about 2 g of soda ash was added over about 0.1 min to about1 min; about 45 g of total fillers (olive pit flour and/or walnut shellflour per respective example, as listed in Table 5) was added over about2 min to about 5 min; about 1 g of surfactant was added over about 0.1min to about 1 min; and about 32 g of aqueous sodium hydroxide solution(about 50 wt % of solid sodium hydroxide and about 50 wt % of water) wasadded over about 2 min to about 4 min. The components of the binder weremixed at a temperature of about 15° C. to about 40° C. The mixture wasagitated for about 2 min to about 3 min, then agitation was stopped. Tothe mixture, about 30 g of pMDI was added over about 1 min to about 3min. The agitator was started. To the mixture, about 30 g of water wasadded over about 1 min to about 5 min, then agitation was stopped, andthe mixture, i.e., the binder composition, was discharged into acontainer.

The binder composition of Exs. 21-30 contained about 90.7 wt % ofphenol-formaldehyde resin solids, about 9.3 wt % of pMDI solids, about19.9 wt % of total extender, about 14.0 wt % of total filler, and about171.0 wt % of water, based on a combined solids weight of thephenol-formaldehyde resin and the pMDI. As such, the binder compositionshad a solids content of about 43.9 wt % and a water content of about56.1 wt %, based on the total weight of the binder. The binders of Exs.21-30 all had a pH of about 11.5 to about 12.3 at a temnerature of about25° C.

TABLE 5 Binder Compositions for Examples 21-30 Extenders Fillers WheatFlour Corn Flour Olive Pit Flour Walnut Shell Flour Ex. (wt %)¹ (wt %)¹(wt %)² (wt %)² 21 100 0 0 100 22 75 25 0 100 23 50 50 0 100 24 25 75 0100 25 0 100 0 100 26 100 0 100 0 27 75 25 100 0 28 50 50 100 0 29 25 75100 0 30 0 100 100 0 ¹wt % based on the combined weight of the corn andwheat flours ²wt % based on the combined weight of the olive pit andwalnut shell flours

Examples 21-30—Binder Viscosities

For the binders of Exs. 21-30, the viscosity was measured and recordedat a temperature of 25° C. on the referenced days for each respectiveexample, as listed in Table 6, starting immediately after the binder wasformed (Day 1). Accordingly, the viscosity values on Day 2 were measured24 hours after the binder was formed, the viscosity values on Day 3 weremeasured 48 hours after the binder was formed, and so on with eachsubsequent day adding another 24 hours of time.

TABLE 6 Binder Viscosities (cP) for Examples 21-30 Days Ex. 1 3 4 7 8 910 11 14 21 1178 3490 4120 — — — — — — 22 780 1850 — 2290 2630 2887 31333447 4340 23 630 1317 — 1510 1847 1930 2117 2400 3073 24 437 745 — 9341050 1122 1195 1322 1643 25 335 487 — 504  602 670  740  845 997 26 6501720 — 2007 — 2150 — — 2303 27 569 1283 — 1410 — 1520 — — 1760 28 394753 — 836 — 930 — — 993 29 331 492 — 558 — 600 — — 673 30 260 309 — 325— 349 — — 384 Days Ex. 15 16 18 21 22 25 26 29 30 21 — — — — — — — — —22 — — — — — — — — — 23 3513 3707 4087 — — — — — — 24 1690 1837 20732450 2880 3547 — 4237 — 25 1145 1183 1373 1693 1903 2287 — 3087 — 26 —2520 2753 2980 — — 3540 — 4010 27 — 1887 2043 2343 — — 2621 — 3024 28 —1000 1037 1102 — — 1257 — 1556 29 — 680 757 789 — — 876 — 934 30 — 414447 498 — — 579 — 646

Surprisingly and unexpectedly the binders of Exs. 22-30 all maintained aviscosity of less than 3,500 cP at a temperature of about 25° C. for atleast 3 days after formation of the binders.

Examples 31-40—Binder Compositions

For Exs. 31-40, each binder was prepared according to the followingprocedure. To a blend tank equipped with an agitator, about 117 g ofwater and about 670 g of phenol-formaldehyde resin were added. Theagitator was started. To the mixture, in the following order and timeframe: about 57 g of total extenders (wheat flour and/or corn flour perrespective example, as listed in Table 7) was added over about 2 min toabout 5 min; about 2 g of soda ash was added over about 0.1 min to about1 min; about 41 g of total fillers (olive pit flour and/or walnut shellflour per respective example, as listed in Table 7) was added over about2 min to about 5 min; about 1 g of surfactant was added over about 0.1min to about 1 min; and about 32 g of aqueous sodium hydroxide solution(about 50 wt % of solid sodium hydroxide and about 50 wt % of water) wasadded over about 2 min to about 4 min. The components of the binder weremixed at a temperature of about 15° C. to about 40° C. The mixture wasagitated for about 2 min to about 3 min, then agitation was stopped. Tothe mixture, about 40 g of pMDI was added over about 1 min to about 3min. The agitator was started. To the mixture, about 40 g of water wasadded over about 1 min to about 5 min, then agitation was stopped, andthe mixture, i.e., the binder composition, was discharged into acontainer.

The binder composition of Exs. 31-40 contained about 87.9 wt % ofphenol-formaldehyde resin solids, about 12.1 wt % of pMDI solids, about17.2 wt % of total extender, about 12.4 wt % of total filler, and about166.4 wt % of water, based on a combined solids weight of thephenol-formaldehyde solids and the pMDI. As such, the bindercompositions had a solids content of about 43.8 wt % and a water contentof about 56.2 wt %, based on the total weight of the binder. The bindersof Exs. 31-40 all had a pH of about 11.5 to about 12.3 at a temperatureof about 25° C.

TABLE 7 Binder Compositions for Examples 31-40 Extenders Fillers WheatFlour Corn Flour Olive Pit Flour Walnut Shell Flour Ex. (wt %)¹ (wt %)¹(wt %)² (wt %)² 31 100 0 0 100 32 75 25 0 100 33 50 50 0 100 34 25 75 0100 35 0 100 0 100 36 100 0 100 0 37 75 25 100 0 38 50 50 100 0 39 25 75100 0 40 0 100 100 0 ¹wt % based on the combined weight of the corn andwheat flours ²wt % based on the combined weight of the olive pit andwalnut shell flours

Examples 31-40—Binder Viscosities

For the binders of Exs. 31-40, the viscosity was measured and recordedat a temperature of 25° C. on the referenced days for each respectiveexample, as listed in Table 8, starting immediately after the binder wasformed (Day 1). Accordingly, the viscosity values on Day 2 were measured24 hours after the binder was formed, the viscosity values on Day 3 weremeasured 48 hours after the binder was formed, and so on with eachsubsequent day adding another 24 hours of time.

TABLE 8 Binder Viscosities (cP) for Examples 31-40 Days Ex. 1 3 6 7 8 910 13 14 31 1467 3673 5500 — — — — — — 32 980 2250 3020 3627 4217 — — —— 33 695 1350 1530 2030 2300 2597 3240 4513 — 34 490 804 946 1160 12101373 1617 2230 2503 35 374 564 646 736  762 874 1047 1413 1597 36 5401793 — 2210 — 2567 — — 3033 37 501 1232 — 1557 — 1770 — — 2060 38 394881 — 1003 — 1127 — — 1357 39 298 502 — 581 — 648 — — 810 40 250 339 —394 — 431 — — 515 Days Ex. 15 16 17 18 20 21 22 26 30 31 — — — — — — — —— 32 — — — — — — — — — 33 — — — — — — — — — 34 2940 — 3360 — 4560 — — —— 35 1853 — 2260 — 3060 3533 4087 — — 36 — 3307 — 3727 — 4433 — — — 37 —2293 — 2567 — 2976 — 3942 4765 38 — 1473 — 1707 — 1978 — 2495 3022 39 —903 — 1033 — 1200 — 1506 1999 40 — 575 — 652 — 828 — 1102 1431

Surprisingly and unexpectedly the binders of Exs. 31-40 all maintained aviscosity of less than 3,500 cP at a temperature of about 25° C. for atleast 1 day after formation of the binders.

Examples 41-50—Binder Compositions

For Exs. 41-50, each binder was prepared according to the followingprocedure. To a blend tank equipped with an agitator, about 108 g ofwater and about 670 g of phenol-formaldehyde resin were added. Theagitator was started. To the mixture, in the following order and timeframe: about 51 g of total extenders (wheat flour and/or corn flour perrespective example, as listed in Table 9) was added over about 2 min toabout 5 min; about 2 g of soda ash was added over about 0.1 min to about1 min; about 36 g of total fillers (olive pit flour and/or walnut shellflour per respective example, as listed in Table 9) was added over about2 min to about 5 min; about 1 g of surfactant was added over about 0.1min to about 1 min; and about 32 g of aqueous sodium hydroxide solution(about 50 wt % of solid sodium hydroxide and about 50 wt % of water) wasadded over about 2 min to about 4 min. The components of the binder weremixed at a temperature of about 15° C. to about 40° C. The mixture wasagitated for about 2 min to about 3 min, then agitation was stopped. Tothe mixture, about 50 g of pMDI was added over about 1 min to about 3min. The agitator was started. To the mixture, about 50 g of water wasadded over about 1 min to about 5 min, then agitation was stopped, andthe mixture, i.e., the binder composition, was discharged into acontainer.

The binder composition of Exs. 41-50 contained about 85.4 wt % ofphenol-formaldehyde resin solids, about 14.6 wt % of the pMDI solids,about 14.9 wt % of total extender, about 10.5 wt % of total filler, andabout 161.8 wt % of water, based on a combined solids weight of thephenol-formaldehyde resin and the pMDI. As such, the binder compositionshad a solids content of about 43.7 wt % and a water content of about56.3 wt %, based on the total weight of the binder. The binders of Exs.41-50 all had a pH of about 11.5 to about 12.3 at a temperature of about25° C.

TABLE 9 Binder Compositions for Examples 41-50 Extenders Fillers WheatFlour Corn Flour Olive Pit Flour Walnut Shell Flour Ex. (wt %)¹ (wt %)¹(wt %)² (wt %)² 41 100 0 0 100 42 75 25 0 100 43 50 50 0 100 44 25 75 0100 45 0 100 0 100 46 100 0 100 0 47 75 25 100 0 48 50 50 100 0 49 25 75100 0 50 0 100 100 0 ¹wt % based on the combined weight of the corn andwheat flours ²wt % based on the combined weight of the olive pit andwalnut shell flours

Examples 41-50—Binder Viscosities

For the binders of Exs. 41-50, the viscosity was measured and recordedat a temperature of 25° C. on the referenced days for each respectiveexample, as listed in Table 10, starting immediately after the binderwas formed (Day 1). Accordingly, the viscosity values on Day 2 weremeasured 24 hours after the binder was formed, the viscosity values onDay 3 were measured 48 hours after the binder was formed, and so on witheach subsequent day adding another 24 hours of time.

TABLE 10 Binder Viscosities (cP) for Examples 41-50 Days Ex. 1 3 5 6 7 89 10 41 1390 6400 — — — — — — 42 951 3513 — 5480 — — — — 43 625 1750 —3033 3667 4303 — — 44 417 948 — 1240 1587 2030 2317 3060 45 365 623 — 875 1061 1212 1533 1837 46 656 — 2827 — 3280 — — — 47 462 — 1833 — 1860— — — 48 399 — 1265 — 1200 — — — 49 318 — 673 — 703 — — — 50 263 — 408 —453 — — — Days Ex. 12 13 14 16 18 21 26 30 41 — — — — — — — — 42 — — — —— — — — 43 — — — — — — — — 44 — 6800 — — — — — — 45 — 3187 4207 — — — —— 46 4680 — — — — — — — 47 2895 — 3333 4370 — — — — 48 1693 — 2263 29333811 4990 — — 49 1000 — 1222 1513 2002 2778 4265 — 50 596 —  728 9381222 1668 2877 3869

Surprisingly and unexpectedly the binders of Exs. 41-50 all maintained aviscosity of less than 3,500 cP at a temperature of about 25° C. for atleast 1 day.

Comparative Examples 1-6—Binder Compositions

For CExs. 1-6, each binder was prepared according to the followingprocedure. Binder compositions were made that did not include anextender or a filler, but varied the amount of pMDI throughout thecomparative examples. For each of CEx. 1-6, to a blend tank equippedwith an agitator, 1,000 g, 990 g, 980 g, 970 g, 960 g, and 950 g,respectively, of phenol-formaldehyde resin (about 43.5 wt %phenol-formaldehyde resin solids) were added to the blend tank. Theagitator was started. To the mixture, in the following order and timeframe: The components of the binder were mixed at a temperature of about15° C. to about 40° C. The mixture was agitated for about 2 min to about3 min, then agitation was stopped. To the mixture, pMDI (none for CEx.1; about 10 g for CEx. 2; about 20 g for CEx. 3; about 30 g for CEx. 4;about 40 g for CEx. 5; and about 50 g for CEx. 6) was added over about 1min to about 3 min. The mixture was agitated for about 1 min to about 5min, then agitation was stopped, and the mixture, i.e., the bindercomposition, was discharged into a container. The binder composition ofCExs. 1-6 contained about 53 wt % of water to about 57 wt % of water,based on the combined weight of the phenol-formaldehyde resin solids,the pMDI solids, and water. The binders of CExs. 1-6 all had a pH ofabout 11.5 to about 12.3 at a temperature of about 25° C.

TABLE 11 Binder Compositions for CExs. 1-6 CEx. PF Resin (wt %)¹ pMDI(wt %)¹ Water Content (wt %)² 1 100 0 56.5 2 97.7 2.3 55.9 3 95.5 4.555.4 4 93.4 6.6 54.8 5 91.3 8.7 54.2 6 89.2 10.8 53.6 ¹wt % based on thecombined solids weight of the PF resin and the pMDI ²wt % based on thecombined weight of water, PF resin solids, and pMDI solids

Comparative Examples 1-6—Binder Viscosities

For the binders of CExs. 1-6, the viscosity was measured and recorded ata temperature of 25° C. on the referenced days for each respectiveexample, as listed in Table 12, starting immediately after the binderwas formed (Day 1). Accordingly, the viscosity values on Day 2 weremeasured 24 hours after the binder was formed, the viscosity values onDay 3 were measured 48 hours after the binder was formed, and so on witheach subsequent day adding another 24 hours of time.

TABLE 12 Binder Viscosities (cP) for CExs. 1-6 Days CEx. 1 2 3 6 7 8 910 13 14 15 30 1 1077 1135 1230 1640 1800 1963 2400 2463 3707 4320 — — 21157 1398 1680 2260 2800 3270 3600 4460 — — — — 3 1133 1694 2110 36604400 — — — — — — — 4 1025 2600 3892 8420 — — — — — — — — 5 1022 36876700 — — — — — — — — — 6 910 4190 — — — — — — — — — —

Comparative Examples 7-11—Binder Compositions

For CExs. 7-11, each binder was prepared according to the followingprocedure. Binder compositions were made that did not include anextender or a filler, but varied the amount of pMDI throughout thecomparative examples. To a blend tank equipped with an agitator, about1,475 g, about 1,423 g, about 1,373 g, about 1,328 g, and about 1,287 gof the phenol-formaldehyde resin (GPR 5815 resin that had a solidscontent of about 43.5 wt %) were added thereto for CExs. 7-11,respectively. The agitator was started and the phenol-formaldehyde resinwas agitated for about 2 min to about 3 min, then agitation was stopped.To the blend tank, the pMDI resin (DESMODUR® 44V20L resin) was addedover about 1 min to about 3 min (about 22 g for CEx. 7; about 42 g forCEx. 8; about 61 g for CEx. 9; about 79 g for CEx. 10; and about 96 gfor CEx. 11). To the mixture, water was added over about 1 min to about5 min (about 4 g for CEx. 7; about 34 g for CEx. 8; about 66 g for CEx.9; about 93 g for CEx. 10; and about 117 g for CEx. 11), then agitationwas stopped, and the mixture, i.e., the binder composition, wasdischarged into a container. The components of the binder were mixed ata temperature of about 15° C. to about 40° C. The binders of CExs. 7-11all had a pH of about 11.3 at a temperature of about 25° C.

TABLE 13 Binder Compositions for CExs. 7-11 CEx. PF Resin (wt %)¹ pMDI(wt %)¹ Water Content (wt %)² 7 96.7 3.3 55.8 8 93.6 6.4 55.9 9 80.7 9.356.1 10 87.9 12.1 56.2 11 85.4 14.6 56.3 ¹wt % based on the combinedsolids weight of the PF resin and the pMDI ²wt % based on the combinedweight of water, PF resin solids, and pMDI solids

Comparative Examples 7-11—Binder Viscosities

For the binders of CExs. 7-11, the viscosity was measured and recordedat a temperature of 25° C. on the referenced days for each respectiveexample, as listed in Table 14, starting immediately after the binderwas formed (Day 1). Accordingly, the viscosity values on Day 2 weremeasured 24 hours after the binder was formed, the viscosity values onDay 3 were measured 48 hours after the binder was formed, and so on witheach subsequent day adding another 24 hours of time.

TABLE 14 Binder Viscosities (cP) for CExs. 7-11 Days CEx. 1 2 3 6 7 8 910 13 14 20 28 7 323 390 451 489 577 634 698 755 831 998 1309 2423 8 270405 501 599 750 849 1008 1244 1555 1810 2985 6253 9 230 370 689 888 13791654 2040 2601 3989 5620 10 195 420 600 2010 3813 5840 11 193 360 13084780

Example 51—Binder Composition

To a blend tank equipped with an agitator, about 14.56 g of water andabout 60.76 g of phenol-formaldehyde resin were added therein. Theagitator was started. To the mixture, in the following order and timeframe: about 3.82 g of wheat flour was added over about 2 min to about 5min; about 2.54 g of corn flour was added over about 2 min to about 5min; about 0.37 g of soda ash was added over about 0.1 min to about 1min; about 3.27 g of nutshell flour was added over about 2 min to about5 min; about 3.27 g of olive pit flour was added over about 1 min toabout 4 min; about 0.13 g of surfactant was added over about 0.1 min toabout 1 min; and about 2.84 g of aqueous sodium hydroxide solution(about 50 wt % of solid sodium hydroxide and about 50 wt % of water) wasadded over about 2 min to about 4 min. The mixture was agitated forabout 2 min to about 3 min, then agitation was stopped. To the mixture,about 4.23 g of pMDI was added over about 1 min to about 3 min. Theagitator was started. To the mixture, about 4.23 g of water was addedover about 1 min to about 5 min, then agitation was stopped, and themixture was discharged into a container.

Table 15 provides a step-wise listing of the components and process usedto make the binder described in Example 51. The components of the binderwere mixed at a temperature of about 15° C. to about 40° C. The binderhad a solids concentration of about 43 wt % to about 46 wt % and a pH ofabout 11.5 to about 12.3 at a temperature of about 25° C.

TABLE 15 Preparation of Binder Ex. 51 Action Component Amount (g) Time(min) add water 14.56  — add PF resin 60.76  — start mix start agitator— — add wheat flour 3.82 2-5 add corn flour 2.54 2-5 add soda ash 0.37 1or less add nutshell flour 3.27 2-5 add olive pit flour 3.27 1-4 addsurfactant 0.13 1 or less add caustic solution (50 wt %) 2.84 2-4 mixcontinue mixing — 2-3 stop mix stop agitator — — add pMDI resin 4.23 1-3start mix start agitator — — add water 4.23 1-5 stop mix stop agitator ——

Example 52—Plywood Preparation

Plywood was made with the binder formulation of Ex. 51. The plywood wasmade as five ply using radiata pine veneer that had a thickness of about3.2 mm and a moisture content of about 7 wt % to about 16 wt %. Thebinder spread was about 15 g/ft² and the binder was applied using anextruder, available from Raute Corporation. Five plies of the veneerwere stacked and pressed in a Wabash press with a platen temperature ofabout 120° C. to about 135° C., at a pressure of about 0 MPa to about1.2 MPa, and for about 4 min to about 8 min to produce the plywood.

The plywood had an IB (vacuum) of about 1.6 N/mm², an IB (boil) of about1.5 N/mm², a wood failure of about 89%, a MOR of about 65 N/mm², a MOEof about 7,000 N/mm², a moisture content of about 9%, and a density ofabout 515 kg/m³.

Examples 53-59 and Comparative Examples 12-18

Preparation and properties of another 14 binders, i.e., Exs. 53-59 andCExs. 12-18, which included higher resin solids as compared to theExamples above were prepared. More particularly, the additional 14binders were prepared by mixing one of five resins (Resin 1, 2, 3, 4, or5), wheat flour as an extender, corn cob residue as a filler, sodiumhydroxide as a base compound, water, and pMDI.

Synthesis of Resin 1 (2.25 F/P mole ratio, 43% total solids, 0% urea,and 6% resin alkalinity). Phenol (2,560.3 g), a 50% aqueous formaldehydesolution (1,307.2 g), and water (2,118.8 g) were added to a 2.5 galreactor equipped with a mechanical stirrer, cooling coils, athermocouple, a heating mantle, and a reflux condenser. The contents ofthe reactor were stirred and the temperature was adjusted to about 50°C. A 50% aqueous NaOH solution (400.0 g) was added evenly over 25minutes while the reaction temperature was allowed to increase to atemperature of about 68° C. An additional amount of the 50% aqueousformaldehyde solution (2,369.2 g) was added evenly over 45 minutes whilethe temperature was allowed to exotherm to about 95° C. After theadditional 50% aqueous formaldehyde solution was added to the reactor,the reaction was held at a temperature of about 95° C. until aGardner-Holdt viscosity of “CD” was reached and was then cooled to atemperature of about 85° C. over 10 minutes. An additional amount of the50% aqueous NaOH solution (400 g) was added over 5 minutes. The reactionwas stirred at a temperature of about 85° C. until a Gardner-Holdtviscosity of “TU” was reached. An additional amount of the 50% aqueousNaOH solution (400 g) was added and the reaction was stirred until aGardner-Holdt viscosity of “WX” was reached. The reaction mixture wascooled to a temperature of about 60° C. over an additional 20 minutes,and water (445.5 g) was added over 5 min and the reaction was cooled to25° C. over an additional 15 minutes to afford a final viscosity ofabout 634 cP and a % caustic of about 5.94.

Synthesis of Resin 2 (2.25 F/P mole ratio, 43% total solids, 8% urea,and 6% resin alkalinity). Phenol (2,172.8 g), a 50% aqueous formaldehydesolution (1,109.3 g), and water (1,907.2 g) were added to a 2.5 galreactor equipped with a mechanical stirrer, cooling coils, athermocouple, a heating mantle, and a reflux condenser. The contents ofthe reactor were stirred and the temperature was adjusted to about 50°C. A 50% aqueous NaOH solution (400 g) was added evenly over 25 minuteswhile the reaction temperature was allowed to increase to about 68° C.An additional amount of the 50% aqueous formaldehyde solution (2,010.7g) was added evenly over 45 minutes while allowing the temperature toexotherm to about 95° C. After the additional 50% aqueous formaldehydesolution was added to the reactor, the reaction was held at atemperature of about 95° C. until a Gardner-Holdt viscosity of “E” wasreached and was then cooled to a temperature of about 85° C. over 10minutes. An additional amount of the 50% aqueous NaOH solution (400 g)was added over 5 minutes. At this point, urea prill (400 g) and water(400 g) were added over 10 minutes. The reaction was stirred at atemperature of about 85° C. until a Gardner-Holdt viscosity of “UV” wasreached. An additional amount of the 50% aqueous NaOH solution (400.0 g)was added and the reaction was allowed to stir until a Gardner-Holdtviscosity of “YZ” was reached. At this point, additional urea prill(400.0 g) and water (400.0 g) were added over 10 minutes while thereaction mixture was cooled to 60° C. over an additional 15 minutes. Thereaction was cooled to 25° C. over an additional 20 minutes to afford afinal viscosity of about 722 cP and a % caustic of about 6.12.

Synthesis of Resin 3 (2.25 F/P mole ratio, 43% total solids, 4% urea,and 6% resin alkalinity). Phenol (1,183.3 g), a 50% aqueous formaldehydesolution (604.2 g), and water (1,117.6 g) were added to a 1.25 galreactor equipped with a mechanical stirrer, cooling coils, athermocouple, a heating mantle, and a reflux condenser. The contents ofthe reactor were stirred and the temperature was adjusted to about 50°C. A 50% aqueous NaOH solution (200 g) was added evenly over 25 minuteswhile the reaction temperature was allowed to increase to a temperatureof about 68° C. An additional amount of the 50% aqueous formaldehydesolution (1,095 g) was added evenly over 45 minutes while allowing thetemperature to exotherm to about 95° C. After the additional 50% aqueousformaldehyde solution was added to the reactor, the reaction was held ata temperature of about 95° C. until a Gardner-Holdt viscosity of “C” wasreached and was then cooled to a temperature of about 85° C. over 10minutes. An additional amount of the 50% aqueous NaOH solution (200 g)was added over 5 minutes. At this point, urea prill (100 g) and water(100 g) were added over 10 minutes. The reaction was stirred at atemperature of about 85° C. until a Gardner-Holdt viscosity of “TU” wasreached. An additional amount of the 50% aqueous NaOH solution (200 g)was added and the reaction was stirred until a Gardner-Holdt viscosityof “W” was reached. At this point, urea prill (100 g) and water (100 g)were added over 10 minutes while the reaction mixture was cooled to 60°C. over an additional 15 minutes. The reaction was cooled to 25° C. overan additional 20 minutes to afford a final viscosity of about 612 cP anda % caustic of about 6.10.

Synthesis of Resin 4 (2.25 F/P mole ratio, 43% total solids, 4% urea,and 6% resin alkalinity). Phenol (1,183.3 g), 50% aqueous formaldehydesolution (604.2 g), and water (895.3 g) were added to a 1.25 gal reactorequipped with a mechanical stirrer, cooling coils, a thermocouple, aheating mantle, and a reflux condenser. The contents of the reactor wasstirred and the temperature was adjusted to about 50° C. A 50% aqueousNaOH solution (200 g) was added evenly over 25 minutes while thereaction temperature was allowed to increase to a temperature of about68° C. An additional amount of the 50% aqueous formaldehyde solution(1,095 g) was added evenly over 45 minutes while the temperature wasallowed to exotherm to about 95° C. After the additional 50% aqueousformaldehyde solution was added to the reactor, the reaction was held ata temperature of about 95° C. until a Gardner-Holdt viscosity of “E” wasreached and was then cooled to a temperature of about 85° C. over 10minutes. An additional amount of the 50% aqueous NaOH solution (200 g)was added over 5 minutes. At this point, urea prill (200.0 g) and water(200.0 g) were added over 10 minutes. The reaction was stirred at atemperature of about 85° C. until a Gardner-Holdt viscosity of “TU” wasreached. An additional amount of the 50% aqueous NaOH solution (200.0 g)was added and the reaction was stirred until a Gardner-Holdt viscosityof “WX” was reached. At this point, water (222.3 g) was added over 5minutes while the reaction mixture was cooled to 60° C. over anadditional 15 minutes. The reaction was cooled to 25° C. over anadditional 20 minutes to afford a final viscosity of about 623 cP and a% caustic of about 6.08.

Synthesis of Resin 5 (2.25 F/P mole ratio, 43% total solids, 4% urea,and 6% resin alkalinity). Phenol (1,183.3 g), a 50% aqueous formaldehydesolution (604.2 g), and water (1117.6.3 g) was added to a 1.25 galreactor equipped with a mechanical stirrer, cooling coils, athermocouple, a heating mantle, and a reflux condenser. The contents ofthe reactor was stirred and the temperature was adjusted to 50° C. A 50%aqueous NaOH solution (200.0 g) was added evenly over 25 minutes whilethe reaction temperature was allowed to increase to a temperature ofabout 68° C. An additional amount of the 50% aqueous formaldehydesolution (1,095 g) was added evenly over 45 minutes while thetemperature was allowed to exotherm to 95° C. After the additional 50%aqueous formaldehyde solution was added to the reactor, the reaction washeld at a temperature of about 95° C. until a Gardner-Holdt viscosity of“C” was reached and then cooled to 85° C. over 10 minutes. An additionalamount of the 50% aqueous NaOH solution (200.0 g) was added over 5minutes. The reaction was stirred at a temperature of about 85° C. untila Gardner-Holdt viscosity of “UV” was reached. An additional amount ofthe 50% aqueous NaOH solution (200.0 g) was added and the reactionstirred until a Gardner-Holdt viscosity of “YZ” was reached. At thispoint, urea prill (200.0 g) and water (200.0 g) were added over 5minutes while the reaction mixture was cooled to 60° C. over anadditional 15 minutes. The reaction was cooled to 25° C. over anadditional 20 minutes to afford a final viscosity of about 622 cP and a% caustic of about 6.06.

The binders in Exs. 53-59 and CExs. 12-18 were then prepared accordingto the steps outlined in Tables 16 and 17.

TABLE 16 CEx. 12 CEx. 13 Ex. 53 Ex. 54 CEx. 14 CEx. 15 Ex. 55 AmountAmount Amount Amount Amount Amount Amount Action ING (g) (g) (g) (g) (g)(g) (g) Add Resin 400 of 400 of 600 of 600 of 250 of 250 of 500 of Resin1 Resin 1 Resin 2 Resin 2 Resin 1 Resin 1 Resin 2 Add Wheat 52 52 52 5228.7 28.7 28.7 Flour Mix 5 5 10 10 5 5 5 (min) Add Water 108.8 112 0 029.1 32.5 29.1 Mix 2 2 0 0 2 2 2 (min) Add Corn- 64.3 64.3 64.3 64.335.7 35.6 35.7 Cob Mix 3 3 6 3 3 3 3 (min) Add 50% 34 34 10 10 26 26 16NaOH Mix 10 15 2 3 15 15 10 (min) Add Resin 320.9 of 297.7 of 120.9 of97.7 of 860.5 of 587.2 of 360.5 of Resin 1 Resin 1 Resin 2 Resin 2 Resin1 Resin 1 Resin 2 Mix 3 3 2 2 3 3 3 (min) Stop Agitator Add 50% 0 0 2424 0 0 10 NaOH Add Water 10 20 118.8 132 10 20 10 Add pMDI 10 20 10 2010 20 10 Mix 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (min)

TABLE 17 Ex. 56 Ex. 57 Ex. 58 Ex. 59 CEx. 16 CEx. 17 CEx. 18 AmountAmount Amount Amount Amount Amount Amount Action ING (g) (g) (g) (g) (g)(g) (g) Add Resin 500 of 400 of 400 of 400 of 400 of 400 of 250 of Resin2 Resin 3 Resin 4 Resin 5 Resin 1 Resin 1 Resin 1 Add Wheat 28.7 40.540.5 40.5 52.0 40.5 28.7 Flour Mix 5 5 5 5 5 5 5 (min) Add Water 32.470.6 70.6 70.6 105.5 65.7 25.9 Mix 2 2 2 2 2 2 2 (min) Add Co- 35.7 49.949.9 49.9 64.3 49.9 35.7 Cob Mix 3 3 3 3 3 3 3 (min) Add 50% 16.0 30.030.0 30.0 34.0 30.0 26.0 NaOH Mix 10 15 15 15 15 15 15 (min) Add Resin337.2 of 379.1 of 379.1 of 379.1 of 344.2 of 414 of 633.7 of Resin 2Resin 3 Resin 4 Resin 5 Resin 1 Resin 1 Resin 1 Mix 3 3 3 3 3 3 3 (min)Stop Agitator Add 50% 10.0 0.0 0.0 0.0 0.0 0.0 0.0 NaOH Add Water 20.015.0 15.0 15.0 0.0 0.0 0.0 Add pMDI 20.0 15.0 15.0 15.0 0.0 0.0 0.0 Mix0.5 0.5 0.5 0.5 0.0 0.0 0.0 (min)

Table 18 summarizes the urea content and solids properties of Exs. 53-59and CExs. 12-18. The “Resin % Urea” indicates the total concentration ofurea. The term “CI” refers to the urea being at least partially “cookedin” to the resin by being reacted into the phenol-formaldehyde resin.More particularly, without wishing to be bound by theory, it is believedthat when the urea was cooked in that the resin formed was aphenol-urea-formaldehyde resin. More particularly, it is believed thatwhen the urea is cooked in that at least a portion of the urea formed acovalent bond with a carbon atom derived from the formaldehyde duringsynthesis of the resin. However, without wishing to be bound by theory,it is also believed that at least some of the urea could be decomposedunder the reaction conditions to form ammonia that could also react withthe phenol-formaldehyde oligomers to form benzylic amine linkages.Either scenario leads to greater molecular weight urea- oramino-modified phenol-formaldehyde resins.

The term “BA” refers to the urea having been “back added” such that theurea is initially “free” urea in the phenol-formaldehyde resin. In someembodiments, over time, at least a portion of the free urea can reactwith at least a portion of any residual free formaldehyde to producemethylol ureas, such as mono-methylol urea, di-methylol urea, ortri-methylol urea, or a mixture thereof.

As noted above, the term “% Total Mix Solids” is the sum of all solidsin the resin. As such, as an example, Resin 1 that included 44% TotalMix Solids contained 56 wt % of water. As noted above, the Total MRSrefers to the total amount of solids contributed only by the pMDI resinand either the phenol-formaldehyde resin or the urea-modifiedphenol-formaldehyde resin, i.e., all of the phenol, formaldehyde, urea(if used), and base compound used to make the phenol-formaldehyde orurea-modified phenol-formaldehyde resin. As shown, in Table 18 below,the phenol-formaldehyde resin and the urea-modified phenol-formaldehyderesin each had a Total MRS that ranged from 32 to 38 and the pMDI MRSranged from 0 to 2.

In looking at Table 18, it can be seen that the binders in CExs. 12-18all included Resin 1, which did not contain any urea. It can also beseen that CExs. 16-18 did not include any isocyanate-based resin and canbe considered as “control” binders as opposed to comparative binders. Itcan also be seen that the binders in Exs. 53-59 each included one ofResins 2-5 that did contain urea and pMDI.

TABLE 18 Urea and Solids Properties Base Resin % % Total Mix Total pMDIPF Example Resin Urea Solids MRS MRS MRS CEx. 12 Resin 1 0 44.0 32 1 31CEx. 13 Resin 1 0 44.0 32 2 30 Ex. 53 Resin 2 8 (4% CI/4% 44.0 32 1 31BA) Ex. 54 Resin 2 8 (4% CI/4% 44.0 32 2 30 BA) CEx. 14 Resin 1 0 45.038 1 37 CEx. 15 Resin 1 0 45.0 38 2 36 Ex. 55 Resin 2 8 (4% CI/4% 45.038 1 37 BA) Ex. 56 Resin 2 8 (4% CI/4% 45.0 38 2 36 BA) Ex. 57 Resin 1 4(2% CI/2% 44.5 35 1.5 33.5 BA) Ex. 58 Resin 4 4 (CI) 44.5 35 1.5 33.5Ex. 59 Resin 5 4 (BA) 44.5 35 1.5 33.5 CEx. 16 Resin 1 0 44.0 32 0 32CEx. 17 Resin 1 0 44.5 35 0 35 CEx. 18 Resin 1 0 45.0 38 0 38

The viscosity stability of the binders in Exs. 53-59 and CExs. 12-18were measured over time. The viscosity was measured and recorded at atemperature of 25° C. on the referenced days for each respectiveexample, as listed in Tables 19 and 20, starting immediately after thebinder was formed (Day 0). Accordingly, the viscosity values on Day 1were measured 24 hours after the binder was formed, the viscosity valueson Day 2 were measured 48 hours after the binder was formed, and so onwith each subsequent day adding another 24 hours of time.

The viscosity of the binders in Exs. 53-59 and CExs 12-18 weredetermined at a temperature of about 25° C. using a Model DV-II+viscometer, commercially available from Brookfield Company, Inc., with anumber 3 spindle. The binders in Exs. 53-59 and CExs. 12-18 weremaintained in at water bath at a temperature of about 25° C., during thedays after the binders were formed and the viscosity was periodicallymeasured and are shown in Tables 19 and 20 below. The binders wereperiodically stirred when stored to reduce or prevent phase separationof the respective binder.

TABLE 19 Viscosity (cP) Over Time Elapsed CEx. CEx. Ex. Ex. CEx. CEx.Ex. Time (days) 12 13 53 54 14 15 55 0  865  785 — — — — — 1 1235  9106580 8660 1570 1750 1770 2 1455 1210 — — 1560 1715 1935 3 1550 1320 — —— — 2010 4 1910 1315 6180 8060 — — — 5 — — 6100 7104 1730 1945 — 6 — —6029 6899 1434 1690 2480 7 1870 1495 — — 1472 1536 3034 8 1306 1242 50697590 — — 2573 9 1229 1306 — — 1472 1920 — 10 — — — — — — 3110 11 14341344 5773 9434 — — — 12 — — 5850 9984 1760 2406 — 13 — — 6144 10290 19072714 3780 14 1715 1626 — — 2022 2931 4032 15 1779 1690 — — — — 4544 161869 1779 — — — — — 17 — — — — — — — 18 — — 7770 17540 — — — 19 — — — —2842 4851 — 20 — — 8320 21300 — — 5030 21 2470 2394 8525 22300 2554 5888— 22 — — 8845 28860 — — 5568 23 2586 2458 — — 3571 7091 5837

TABLE 20 Viscosity (cP) Over Time of Binders 8-14 Elapsed Ex. Ex. Ex.Ex. CEx. CEx. CEx. Time (days) 56 57 58 59 16 17 18 0 — — — — — — — 11710 1390 1017 1025 1055  785 1940 2 1930 1400 1230 1250 1270  930 19203 1995 1420 1275 1235 1255  940 — 4 — 1395 1270 1160 1235  950 — 5 — — —— — — 2130 6 2435 — — — — — 1741 7 2995 1660 1500 1630 1400 1040 1715 82790 1715 1626 1280 1229 1075 — 9 — 1600 1331 1254 1242 1075 1754 103418 — — — — — — 11 — 1754 1600 1331 1254 1114 — 12 — — — — — — 1818 134134 — — — — — 1907 14 4352 1946 1779 1434 1267 1139 1971 15 4762 19581882 1485 1318 1165 — 16 — 2086 1958 1536 1357 1190 — 17 — — — — — — —18 — — — — — — — 19 — — — — — — 2355 20 6746 — — — — — — 21 — 2547 24961818 1549 1344 2509 22 8640 — — — — — — 23 8819 2790 2675 2010 1626 14722586

As can be seen in Tables 19 and 20, the binders of Exs. 53 and 55-59each maintained a viscosity of less than 10,000 cP for the 23 days theviscosities were measured. As can also be seen, the binder of Ex. 54maintained a viscosity of less than 10,000 cP for 12 days. Structuralcomposite lumber can be manufactured with the inventive binders 3, 4,and 7-11.

Embodiments of the present disclosure further relate to any one or moreof the following paragraphs:

1. A binder for making composite lignocellulose products, comprising:about 70 wt % to about 99.7 wt % of at least one aldehyde-based resin;about 0.3 wt % to about 30 wt % of at least one isocyanate-based resin;about 10 wt % to about 63 wt % of at least one extender; and about 145wt % to about 230 wt % of water, wherein all weight percent values arebased on a combined solids weight of the aldehyde-based resin and theisocyanate-based resin, and wherein the binder has a viscosity of about200 cP to about 3,500 cP at a temperature of about 25° C. for at leastthe first 12 hours after formation of the binder.

2. A method for making a composite product, comprising: combining aplurality of lignocellulose substrates and a binder to produce aresinated furnish, wherein the binder comprises about 70 wt % to about99.7 wt % of at least one aldehyde-based resin; about 0.3 wt % to about30 wt % of at least one isocyanate-based resin; about 10 wt % to about63 wt % of at least one extender; and about 145 wt % to about 230 wt %of water, wherein all weight percent values are based on a combinedsolids weight of the aldehyde-based resin and the isocyanate-basedresin; and heating the resinated furnish to a temperature of about 60°C. to about 300° C. to at least partially cure the binder to produce acomposite lignocellulose product, wherein each of the plurality oflignocellulose substrates has a moisture content of at least 10 wt % toabout 40 wt %, based on a dry weight of the plurality of lignocellulosesubstrates, when the resinated furnish is heated to the temperature ofabout 60° C. or greater.

3. A resinated furnish, comprising: a plurality of lignocellulosesubstrates and a binder, wherein each of the plurality of lignocellulosesubstrates has a water content of 10 wt % to about 40 wt %, based on adried weight of the plurality of lignocellulose substrates, wherein thebinder comprises about 70 wt % to about 99.7 wt % of at least onealdehyde-based resin; about 0.3 wt % to about 30 wt % of at least oneisocyanate-based resin; about 10 wt % to about 63 wt % of at least oneextender; and about 145 wt % to about 230 wt % of water, wherein allweight percent values are based on a combined solids weight of thealdehyde-based resin and the isocyanate-based resin, and wherein thebinder has a viscosity of about 200 cP to about 3,500 cP at atemperature of about 25° C. for at least the first 12 hours afterformation of the binder.

4. The binder, the method, or the resinated furnish according to any oneof paragraphs 1 to 3, wherein the binder comprises about 71 wt % toabout 99.7 wt % of the aldehyde-based resin; about 0.3 wt % to about 29wt % of the isocyanate-based resin; about 10 wt % to about 63 wt % ofthe extender; and about 145 wt % to about 230 wt % of the water, whereinall weight percent values are based on the combined solids weight of thealdehyde-based resin and the isocyanate-based resin.

5. The binder, the method, or the resinated furnish according to any oneof paragraphs 1 to 4, wherein the binder comprises about 79 wt % toabout 98.5 wt % of the aldehyde-based resin; about 1.5 wt % to about 21wt % of the isocyanate-based resin; about 13.5 wt % to about 51 wt % ofthe extender; and about 159 wt % to about 207 wt % of the water, whereinall weight percent values are based on the combined solids weight of thealdehyde-based resin and the isocyanate-based resin.

6. The binder, the method, or the resinated furnish according to any oneof paragraphs 1 to 5, wherein the binder comprises about 85 wt % toabout 97 wt % of the aldehyde-based resin; about 3 wt % to about 15 wt %of the isocyanate-based resin; about 14.5 wt % to about 26 wt % of theextender; and about 159 wt % to about 207 wt % of the water, wherein allweight percent values are based on the combined solids weight of thealdehyde-based resin and the isocyanate-based resin.

7. The binder, the method, or the resinated furnish according to any oneof paragraphs 1 to 6, wherein the binder further comprises about 5.5 wt% to about 45 wt % of at least one filler, based on the combined solidsweight of the aldehyde-based resin and the isocyanate-based resin.

8. The binder, the method, or the resinated furnish according to any oneof paragraphs 1 to 6, wherein the binder further comprises about 8 wt %to about 37 wt % of at least one filler, based on the combined solidsweight of the aldehyde-based resin and the isocyanate-based resin.

9. The binder, the method, or the resinated furnish according to any oneof paragraphs 1 to 6, wherein the binder further comprises about 9 wt %to about 25 wt % of at least one filler, based on the combined solidsweight of the aldehyde-based resin and the isocyanate-based resin.

10. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 6, wherein the binder further comprises about 10wt % to about 19 wt % of at least one filler, based on the combinedsolids weight of the aldehyde-based resin and the isocyanate-basedresin.

11. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 3, wherein the binder further comprises at leastone filler, and wherein the binder comprises about 85.4 wt % to about96.7 wt % of the aldehyde-based resin; about 3.3 wt % to about 14.6 wt %of the isocyanate-based resin; about 14.9 wt % to about 25.5 wt % of theextender; about 10.5 wt % to about 18.2 of the filler, and about 161.8wt % to about 181.6 wt % of the water, wherein all weight percent valuesare based on the combined solids weight of the aldehyde-based resin andthe isocyanate-based resin.

12. The binder, the method, or the resinated furnish according to anyone of paragraphs 7 to 11, wherein the filler comprises nut shell media,corn media, furfural residues, seed shell media, fruit pit media, animalbones, milwhite, clays, glasses, inorganic oxides, wood flour, groundbark, or any mixture thereof.

13. The binder, the method, or the resinated furnish according to anyone of paragraphs 7 to 11, wherein the filler comprises a nutshellflour, a fruit pit flour, or a mixture thereof.

14. The binder, the method, or the resinated furnish according to anyone of paragraphs 7 to 11, wherein the filler comprises olive pit flour,walnut shell flour, or a mixture thereof.

15. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 14, wherein the extender comprises one or moreflours, spray dried blood, or any mixture thereof.

16. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 15, wherein the extender comprises wheat flour,corn flour, or a mixture thereof.

17. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 16, wherein the aldehyde-based resin comprises aphenol-formaldehyde resin, a urea-formaldehyde resin, amelamine-formaldehyde resin, a melamine-urea-formaldehyde resin, aphenol-melamine-formaldehyde resin, a resorcinol-formaldehyde resin, aphenol-resorcinol-formaldehyde resin, or any mixture thereof.

18. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 17, wherein the isocyanate-based resin comprisespolymeric methylene diphenyl diisocyanate.

19. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 18, wherein the aldehyde-based resin comprises aphenol-formaldehyde resin.

20. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 19, wherein the binder further comprises about0.01 wt % to about 1 wt % of at least one surfactant, based on thecombined solids weight of the aldehyde-based resin and theisocyanate-based resin.

21. The binder, the method, or the resinated furnish according toparagraph 20, wherein the surfactant comprises ethylene glycol, anacetylenic diol compound, or a mixture thereof.

22. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 21, wherein the binder has a free formaldehydeconcentration of less than 0.2 wt %, based on the combined solids weightof the aldehyde-based resin and the isocyanate-based resin.

23. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 22, wherein the binder further comprises about 1wt % to about 5 wt % of at least one hydroxide, based on the combinedsolids weight of the aldehyde-based resin and the isocyanate-basedresin.

24. The binder, the method, or the resinated furnish according toparagraph 23, wherein the hydroxide comprises sodium hydroxide,potassium hydroxide, calcium hydroxide, lithium hydroxide, ammoniumhydroxide, or any mixture thereof.

25. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 24, wherein the binder further comprises about0.1 wt % to about 3 wt % of at least one carbonate, based on thecombined solids weight of the aldehyde-based resin and theisocyanate-based resin.

26. The binder, the method, or the resinated furnish according toparagraph 25, wherein the carbonate comprises sodium carbonate,potassium carbonate, calcium carbonate, lithium carbonate, ammoniumcarbonate, or any mixture thereof.

27. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 26, wherein the binder has a pH of about 10.5 toabout 13.0.

28. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 27, wherein the binder has a viscosity of about200 cP to about 3,500 cP at a temperature of about 25° C. for at least 1day to about 30 days after formation of the binder.

29. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 28, wherein the binder has a viscosity of about300 cP to about 3,250 cP at a temperature of about 25° C. for at least 1day to about 30 days after formation of the binder.

30. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 29, wherein the binder has a viscosity of about400 cP to about 3,000 cP at a temperature of about 25° C. for about 2days to about 30 days after formation of the binder.

31. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 27, wherein the binder has a viscosity of lessthan 3,500 cP for at least 1 day after formation of the binder.

32. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 27, wherein the binder has a viscosity of lessthan 3,500 cP for at least 3 days after formation of the binder.

33. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 27, wherein the binder has a viscosity of lessthan 3,500 cP for at least 5 days after formation of the binder.

34. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 27, wherein the binder has a viscosity of lessthan 3,500 cP for at least 8 days after formation of the binder.

35. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 27, wherein the binder has a viscosity of lessthan 3,500 cP for at least 12 days after formation of the binder.

36. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 27, wherein the binder has a viscosity of lessthan 3,500 cP for at least 15 days after formation of the binder.

37. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 27, wherein the binder has a viscosity of lessthan 3,500 cP for at least 18 days after formation of the binder.

38. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 27, wherein the binder has a viscosity of lessthan 3,500 cP for at least 20 days after formation of the binder.

39. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 27, wherein the binder has a viscosity of lessthan 3,500 cP for at least 23 days after formation of the binder.

40. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 27, wherein the binder has a viscosity of lessthan 3,500 cP for at least 25 days after formation of the binder.

41. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 27, wherein the binder has a viscosity of lessthan 3,500 cP for at least 27 days after formation of the binder.

42. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 27, wherein the binder has a viscosity of lessthan 3,500 cP for at least 30 days after formation of the binder.

43. The method or the resinated furnish according to any one ofparagraphs 2 to 42, wherein each of the plurality of lignocellulosesubstrates has a water content of about 12 wt % to about 30 wt %, basedon a dried weight of the lignocellulose substrates.

44. The method according to any one of paragraphs 2 and 4 to 42, whereineach of the plurality of lignocellulose substrates has a water contentof about 12 wt % to about 30 wt %, based on a dried weight of thelignocellulose substrates when the resinated furnish is heated to thetemperature of about 60° C. or greater.

45. The method or the resinated furnish according to any one ofparagraphs 2 to 44, wherein the plurality of lignocellulose substratescomprise a core disposed between a first outer layer and a second outerlayer; wherein a first amount of the binder is disposed between the coreand the first outer layer, and wherein a second amount of the binder isdisposed between the core and the second outer layer.

46. The method or the resinated furnish according to paragraph 45,wherein the core comprises a first veneer, the first outer layercomprises a second veneer, and the second outer layer comprises a thirdveneer.

47. A method for making a composite product, comprising: combining aplurality of lignocellulose substrates and a binder to produce aresinated furnish, wherein the plurality of lignocellulose substrateshas a moisture content of at least 9 wt % to about 40 wt %, based on adry weight of the plurality of lignocellulose substrates, and whereinthe binder comprises about 70 wt % to about 99.7 wt % of analdehyde-based resin; about 0.3 wt % to about 30 wt % of anisocyanate-based resin; about 10 wt % to about 63 wt % of an extender;and about 145 wt % to about 230 wt % of water, wherein the weightpercent values of the aldehyde-based resin, the isocyanate-based resin,the extender, and the water are based on a combined solids weight of thealdehyde-based resin and the isocyanate-based resin; and heating theresinated furnish to a temperature of about 60° C. to about 300° C. toat least partially cure the binder to produce a composite lignocelluloseproduct, wherein the moisture content of the plurality of lignocellulosesubstrates is at least 10 wt % to about 40 wt %, based on the dry weightof the plurality of lignocellulose substrates, when the resinatedfurnish is heated to the temperature of about 60° C. to about 300° C.

48. The method according to paragraph 47, wherein the moisture contentof the plurality of lignocellulose substrates is about 12 wt % to about40 wt %, based on the dry weight of the plurality of lignocellulosesubstrates, when the resinated furnish is heated to the temperature ofabout 60° C. to about 300° C.

49. The method according to paragraph 47 and 48, wherein thealdehyde-based resin comprises a phenol-formaldehyde resin, and whereinthe isocyanate-based resin comprises polymeric methylene diphenyldiisocyanate.

50. The method according to any one of paragraphs 47 to 48, wherein thebinder further comprises about 1 wt % to about 5 wt % of a hydroxide andabout 0.1 wt % to about 3 wt % of a carbonate, based on the combinedsolids weight of the aldehyde-based resin and the isocyanate-basedresin.

51. The method according to paragraph 50, wherein the hydroxidecomprises sodium hydroxide, potassium hydroxide, calcium hydroxide,lithium hydroxide, ammonium hydroxide, or any mixture thereof.

52. The method according to any one of paragraphs 47 to 51, wherein thebinder further comprises about 0.1 wt % to about 3 wt % of a carbonate,based on the combined solids weight of the aldehyde-based resin and theisocyanate-based resin.

53. The method according to paragraph 52, wherein the carbonatecomprises sodium carbonate, potassium carbonate, calcium carbonate,lithium carbonate, ammonium carbonate, or any mixture thereof.

54. The method according to any one of paragraphs 47 to 53, wherein theextender comprises wheat flour, corn flour, or a mixture thereof.

55. The method according to any one of paragraphs 47 to54, wherein thebinder further comprises about 5.5 wt % to about 45 wt % of a filler,based on the combined solids weight of the aldehyde-based resin and theisocyanate-based resin.

56. The method according to any one of paragraphs 47 to 55, wherein theextender comprises wheat flour, corn flour, or a mixture thereof.

57. The method according to any one of paragraphs 47 to 56, wherein thealdehyde-based resin comprises a phenol-formaldehyde resin.

58. The method according to any one of paragraphs 47 to 57, wherein theisocyanate-based resin comprises polymeric methylene diphenyldiisocyanate.

59. The method according to any one of paragraphs 55 to 58, wherein thefiller comprises a nutshell flour, olive pit flour, or a mixturethereof.

60. The method according to any one of paragraphs 55 to 59, wherein thebinder comprises about 85 wt % to about 97 wt % of the aldehyde-basedresin; about 3 wt % to about 15 wt % of the isocyanate-based resin;about 12 wt % to about 30 wt % of the extender; about 10 wt % to about20 wt % of the filler, and about 150 wt % to about 190 wt % of water,wherein the weight percent values of the aldehyde-based resin, theisocyanate-based resin, the extender, the filler, and the water arebased on a combined solids weight of the aldehyde-based resin and theisocyanate-based resin.

61. The method according to any one of paragraphs 47 to 60, wherein thealdehyde-based resin comprises a phenol-formaldehyde resin having amolar ratio of formaldehyde to phenol of about 2.1:1 to about 2.5:1.

62. The method according to any one of paragraphs 47 to 61, whereinisocyanate-based resin comprises polymeric methylene diphenyldiisocyanate.

63. The method according to any one of paragraphs 47 to 62, whereinextender comprises wheat flour, corn flour, or a mixture thereof.

64. The method according to any one of paragraphs 47 to 63, wherein thenutshell flour comprises walnut shell flour.

65. The method according to any one of paragraphs 47 to 64, wherein: thebinder further comprises about 5.5 wt % to about 45 wt % of a filler,about 0.1 wt % to about 3 wt % of a carbonate, and about 0.1 wt % toabout 2 wt % of a nonionic surfactant, wherein all weight percent valuesare based on a combined solids weight of the aldehyde-based resin andthe isocyanate-based resin, the aldehyde-based resin comprises aphenol-formaldehyde resin having a molar ratio of formaldehyde to phenolof about 2.1:1 to about 2.5:1, the isocyanate-based resin comprisespolymeric methylene diphenyl diisocyanate, the extender comprises wheatflour, corn flour, or a mixture thereof, the filler comprises olive pitflour, walnut shell flour, or a mixture thereof, the carbonate comprisessodium carbonate (e.g., soda ash), potassium carbonate, calciumcarbonate.

66. The method according to any one of paragraphs 47 to 65, wherein thebinder has a viscosity of about 200 cP to about 3,500 cP at atemperature of about 25° C. for at least 1 day to about 30 days afterformation of the binder.

67. The method according to any one of paragraphs 47 to 65, wherein thebinder has a viscosity of about 300 cP to about 3,250 cP at atemperature of about 25° C. for at least 1 day to about 30 days afterformation of the binder.

68. The method according to any one of paragraphs 47 to 65, wherein thebinder has a viscosity of about 400 cP to about 3,000 cP at atemperature of about 25° C. for about 2 days to about 30 days afterformation of the binder.

69. The method according to any one of paragraphs 47 to 65, wherein thebinder has a viscosity of less than 3,500 cP for at least 1 day afterformation of the binder.

70. The method according to any one of paragraphs 47 to 65, wherein thebinder has a viscosity of less than 3,500 cP for at least 3 days afterformation of the binder.

71. The method according to any one of paragraphs 47 to 65, wherein thebinder has a viscosity of less than 3,500 cP for at least 5 days afterformation of the binder.

72. The method according to any one of paragraphs 47 to 65, wherein thebinder has a viscosity of less than 3,500 cP for at least 8 days afterformation of the binder.

73. The method according to any one of paragraphs 47 to 65, wherein thebinder has a viscosity of less than 3,500 cP for at least 12 days afterformation of the binder.

74. The method according to any one of paragraphs 47 to 65, wherein thebinder has a viscosity of less than 3,500 cP for at least 15 days afterformation of the binder.

75. The method according to any one of paragraphs 47 to 65, wherein thebinder has a viscosity of less than 3,500 cP for at least 18 days afterformation of the binder.

76. The method according to any one of paragraphs 47 to 65, wherein thebinder has a viscosity of less than 3,500 cP for at least 20 days afterformation of the binder.

77. The method according to any one of paragraphs 47 to 65, wherein thebinder has a viscosity of less than 3,500 cP for at least 23 days afterformation of the binder.

78. The method according to any one of paragraphs 47 to 65, wherein thebinder has a viscosity of less than 3,500 cP for at least 25 days afterformation of the binder.

79. The method according to any one of paragraphs 47 to 65, wherein thebinder has a viscosity of less than 3,500 cP for at least 27 days afterformation of the binder.

80. The method according to any one of paragraphs 47 to 65, wherein thebinder has a viscosity of less than 3,500 cP for at least 30 days afterformation of the binder.

81. The method according to any one of paragraphs 47 to 80, wherein thebinder has a viscosity of about 200 cP to about 3,500 cP at atemperature of about 25° C. when combined with the plurality oflignocellulose substrates to produce the resinated furnish.

82. The method according to any one of paragraphs 47 to 81, wherein thebinder is made at least the first 12 hours before the binder is combinedwith the plurality of lignocellulose substrates to produce the resinatedfurnish.

83. The method according to any one of paragraphs 47 to 80, wherein thebinder has a viscosity of about 200 cP to about 3,500 cP at atemperature of about 25° C. when combined with the plurality oflignocellulose substrates to produce the resinated furnish, and whereinthe binder is combined with the plurality of lignocellulose substratesat least 12 hours, at least 1 day, at least 2 days, or at least 3 daysto about 10 days, about 15 days, about 20 days, or about 30 days afterat least the aldehyde-based resin, the isocyanate-based resin, theextender, and the water are combined to produce the binder.

84. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 83, wherein the aldehyde-based resin is notprotected or blocked.

85. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 84, wherein the isocyanate-based resin is notprotected or blocked.

86. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 83, wherein the aldehyde-based resin is at leastsubstantially free of any intentional chemical modification intended toprotect or block functional groups thereof.

87. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 83 and 86, wherein the isocyanate-based resin isat least substantially free of any intentional chemical modificationintended to protect or block functional groups thereof.

88. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 83, wherein the aldehyde-based resin issubstantially free of any protected groups that can be deprotected underreactive conditions.

89. The binder, the method, or the resinated furnish according to anyone of paragraphs 1 to 83 and 88, wherein the isocyanate-based resin issubstantially free of any protected groups that can be deprotected underreactive conditions.

90. A binder for making composite lignocellulose products, comprising:about 30 wt % to about 40 wt % of solids comprising a urea-modifiedaldehyde-based resin; about 0.1 wt % to about 3 wt % of solidscomprising an isocyanate-based resin; about 0.1 wt % to about 12 wt % ofan extender; and about 50 wt % to about 62 wt % of a liquid medium,wherein all weight percent values are based on a total weight of thebinder, and wherein the binder has a sodium hydroxide equivalent weightalkalinity of about 3 wt % to about 9 wt %.

91. A method for making a composite product, comprising: combining aplurality of lignocellulose substrates and a binder to produce aresinated furnish, wherein the binder comprises: about 30 wt % to about40 wt % of solids comprising a urea-modified aldehyde-based resin; about0.1 wt % to about 3 wt % of solids comprising an isocyanate-based resin;about 0.1 wt % to about 12 wt % of an extender; and about 50 wt % toabout 62 wt % of a liquid medium, wherein all weight percent values arebased on a total weight of the binder, and wherein the binder has asodium hydroxide equivalent weight alkalinity of about 3 wt % to about 9wt %; and heating the resinated furnish to a temperature of about 60° C.to about 300° C. to at least partially cure the binder to produce acomposite lignocellulose product.

92. A method for making a binder, comprising: contacting solidscomprising a urea-modified aldehyde-based resin, an isocyanate-basedresin, an extender, and a liquid medium to produce the binder, whereinthe binder comprises: about 30 wt % to about 40 wt % of solidscomprising the urea-modified aldehyde-based resin; about 0.1 wt % toabout 3 wt % of solids comprising the isocyanate-based resin; about 0.1wt % to about 12 wt % of the extender; and about 50 wt % to about 62 wt% of the liquid medium, wherein all weight percent values are based on atotal weight of the binder, and wherein the binder has a sodiumhydroxide equivalent weight alkalinity of about 3 wt % to about 9 wt %.

93. The binder or method according to any one of paragraphs 90 to 92,wherein the binder comprises about 0.1 wt % to about 9.5 wt % of freeurea, mono-methylol urea, di-methylol urea, tri-methylol urea, ureareacted into the aldehyde-based resin, or a mixture thereof, based onthe total weight of the binder.

94. The binder or method according to any one of paragraphs 90 to 93,wherein at least a portion of urea in the urea-modified aldehyde-basedresin is in the form of free urea, mono-methylol urea, di-methylol urea,or tri-methylol urea, or a mixture thereof.

95. The binder or method according to any one of paragraphs 90 to 94,wherein at least a portion of the urea in the urea-modifiedaldehyde-based resin is covalently bonded with a carbon atom derivedfrom the aldehyde during synthesis of the urea-modified aldehyde-basedresin.

96. The binder or method according to any one of paragraphs 90 to 95,wherein the urea-modified aldehyde-based resin comprises a urea-modifiedphenol-formaldehyde resin, a urea-modified melamine-formaldehyde resin,a urea-modified phenol-melamine-formaldehyde resin, a urea-modifiedresorcinol-formaldehyde resin, a urea-modifiedphenol-resorcinol-formaldehyde resin, or any mixture thereof.

97. The binder or method according to any one of paragraphs 90 to 96,wherein the urea-modified aldehyde-based resin comprises a urea-modifiedphenol-formaldehyde resin having a formaldehyde to phenol molar ratio ofabout 1.8:1 to about 2.6:1, and wherein the binder comprises: about 32wt % to about 38 wt % of the solids comprising the urea-modifiedaldehyde-based resin, about 1 wt % to about 2 wt % of the solidscomprising the isocyanate-based resin, about 2.9 wt % to about 5.2 wt %of the extender, and about 53 wt % to about 58 wt % of the liquidmedium, wherein all weight percent values are based on the total weightof the binder, and wherein the sodium hydroxide equivalent weightalkalinity of the binder is about 4.5 wt % to about 7.5 wt %.

98. The binder or method according to any one of paragraphs 90 to 97,wherein at least a portion of urea in the urea-modified phenol-aldehyderesin is covalently bonded with a carbon atom derived from the aldehydeduring synthesis of the urea-modified aldehyde-based resin and whereinat least a portion of urea in the urea-modified phenol-aldehyde resinis: (i) in the form of free urea, (ii) in the form of mono-methylolurea, (iii) in the form of di-methylol urea, (iv) in the form oftri-methylol urea, or (v) a mixture thereof.

99. The binder or method according to any one of paragraphs 90 to 98,wherein the binder comprises sodium hydroxide, potassium hydroxide,lithium hydroxide, sodium carbonate, potassium carbonate, calciumcarbonate, sodium borate, potassium borate, calcium borate, and zincborate, or a mixture thereof.

100. The binder or method according to any one of paragraphs 90 to 99,wherein the binder has a viscosity of ≤8,500 cP when maintained at atemperature of about 25° C. for at least 8 days after formation of thebinder.

101. The binder or method according to any one of paragraphs 90 to 100,wherein the binder has a pH of about 11.5 to about 12.5.

102. The binder or method according to any one of paragraphs 90 to 101,wherein the extender comprises wheat flour, corn flour, or a mixturethereof, a

103. The binder or method according to any one of paragraphs 90 to 102,wherein the binder further comprises about 0.1 wt % to about 12 wt % ofa filler, based on the total weight of the binder.

104. The binder or method according to paragraph 103, wherein the fillercomprises corn cob residue, a nutshell flour, a fruit pit flour, or amixture thereof.

105. The binder or method according to any one of paragraphs 90 to 104,wherein the sodium hydroxide equivalent weight alkalinity of the binderis about 5.5% to about 7%.

106. The binder or method according to any one of paragraphs 90 to 105,wherein the binder further comprises about 0.01 wt % to about 0.5 wt %of a surfactant, based on the total weight of the binder.

107. The binder or method according to any one of paragraphs 90 to 106,wherein the binder further comprises a salt.

108. The binder or method according to paragraph 107, wherein the bindercomprises about 0.05 wt % to about 3.5 wt % of the salt, based on thetotal weight of the binder.

109. The binder or method of paragraph 107 or 108, wherein the saltcomprises sodium chloride, potassium chloride, calcium chloride, sodiumsulfate, potassium sulfate, calcium sulfate, magnesium sulfate, or amixture thereof.

110. The binder or method according to any of paragraphs 90 to 109,further comprising about 0.1 wt % to about 12 wt % of a filler, based onthe total weight of the binder, wherein: the urea-modifiedaldehyde-based resin comprises a urea-modified phenol-formaldehyde resinhaving a formaldehyde to phenol molar ratio of about 1.8:1 to about2.6:1, at least a portion of urea in the urea-modifiedphenol-formaldehyde resin is: (i) covalently bonded with a carbon atomderived from the aldehyde during synthesis of the urea-modifiedaldehyde-based resin, (ii) in the form of mono-methylol urea, (iii) inthe form of di-methylol urea, (iv) in the form of tri-methylol urea, or(v) a mixture thereof.

111. The binder or method according to any of paragraphs 90 to 110,wherein the urea-modified aldehyde-based resin comprises aphenol-urea-formaldehyde resin having a formaldehyde to phenol molarratio of about 1.2:1 to about 4:1.

112. The binder or method according to any of paragraphs 90 to 111,wherein the urea-modified aldehyde-based resin comprises aphenol-urea-formaldehyde resin having a formaldehyde to urea molar ratioof about 3.7:1 to about 150:1.

113. The binder or method according to any of paragraphs 90 to 112,wherein the urea-modified aldehyde-based resin comprises aphenol-urea-formaldehyde resin having a phenol to urea molar ratio ofabout 1.5:1 to about 163.4:1.

114. The binder or method according to any of paragraphs 90 to 113,wherein the liquid medium comprises water, an alcohol, an ether, or amixture thereof.

115. The binder or method according to any of paragraphs 90 to 114,wherein the liquid medium comprises water.

116. The binder or method according to any of paragraphs 90 to 115,wherein the urea-modified aldehyde-based resin comprises a urea-modifiedphenol-formaldehyde resin, and wherein during synthesis of theurea-modified phenol-formaldehyde resin at least a portion of the ureadecomposes to produce ammonia, and wherein at least a portion of theammonia reacts with phenol-formaldehyde oligomers to form benzylic aminelinkages.

117. The binder or method according to any of paragraphs 90 to 116,wherein the isocyanate-based resin comprises polymeric methylenediphenyl diisocyanate.

118. The method according to any of paragraphs 91 or 93 to 117, whereinthe composite lignocellulose product comprises structural compositelumber.

119. The method according to paragraph 118, wherein the structuralcomposite lumber comprises laminated veneer lumber, parallel strandlumber, laminated strand lumber, or oriented strand lumber.

120. The method according to paragraph 118 or 119, wherein thestructural composite lumber satisfies the properties as measuredaccording to ASTM D5456-19.

121. The method according to any of paragraphs 91 or 93 to 120, whereinthe plurality of lignocellulose substrates comprises at least 10 wt %,at least 12 wt %, at least 14 wt %, at least 16 wt %, at least 18 wt %,at least 20 wt %, or at least 22 wt % to about 30 wt %, about 35 wt %,or about 40 wt % of water, based on a dry weight of the plurality oflignocellulose substrates.

Certain embodiments and features have been described using a set ofnumerical upper limits and a set of numerical lower limits. It should beappreciated that ranges including the combination of any two values,e.g., the combination of any lower value with any upper value, thecombination of any two lower values, and/or the combination of any twoupper values are contemplated unless otherwise indicated. Certain lowerlimits, upper limits and ranges appear in one or more claims below. Allnumerical values are “about” or “approximately” the indicated value, andtake into account experimental error and variations that would beexpected by a person having ordinary skill in the art.

Various terms have been defined above. To the extent a term used in aclaim is not defined above, it should be given the broadest definitionpersons in the pertinent art have given that term as reflected in atleast one printed publication or issued patent. Furthermore, allpatents, test procedures, and other documents cited in this applicationare fully incorporated by reference to the extent such disclosure is notinconsistent with this application and for all jurisdictions in whichsuch incorporation is permitted.

While the foregoing is directed to embodiments of the present invention,other and further embodiments of the invention may be devised withoutdeparting from the basic scope thereof, and the scope thereof isdetermined by the claims that follow.

What is claimed is:
 1. A binder for making composite lignocelluloseproducts, comprising: about 30 wt % to about 40 wt % of solidscomprising a urea-modified aldehyde-based resin; about 0.1 wt % to about3 wt % of solids comprising an isocyanate-based resin; about 0.1 wt % toabout 12 wt % of an extender; and about 50 wt % to about 62 wt % of aliquid medium, wherein all weight percent values are based on a totalweight of the binder, and wherein the binder has a sodium hydroxideequivalent weight alkalinity of about 3 wt % to about 9 wt %.
 2. Thebinder of claim 1, wherein the binder comprises about 0.1 wt % to about9.5 wt % of free urea, mono-methylol urea, di-methylol urea,tri-methylol urea, urea reacted into the aldehyde-based resin, or amixture thereof, based on the total weight of the binder.
 3. The binderof claim 1, wherein at least a portion of urea in the urea-modifiedaldehyde-based resin is in the form of free urea, mono-methylol urea,di-methylol urea, or tri-methylol urea, or a mixture thereof.
 4. Thebinder of claim 1, wherein at least a portion of urea in theurea-modified aldehyde-based resin is covalently bonded with a carbonatom derived from the aldehyde during synthesis of the urea-modifiedaldehyde-based resin.
 5. The binder of claim 1, wherein theurea-modified aldehyde-based resin comprises a urea-modifiedphenol-formaldehyde resin, a urea-modified melamine-formaldehyde resin,a urea-modified phenol-melamine-formaldehyde resin, a urea-modifiedresorcinol-formaldehyde resin, a urea-modifiedphenol-resorcinol-formaldehyde resin, or any mixture thereof.
 6. Thebinder of claim 1, wherein the urea-modified aldehyde-based resincomprises a urea-modified phenol-formaldehyde resin having aformaldehyde to phenol molar ratio of about 1.8:1 to about 2.6:1, andwherein the binder comprises: about 32 wt % to about 38 wt % of thesolids comprising the urea-modified aldehyde-based resin, about 1 wt %to about 2 wt % of the solids comprising the isocyanate-based resin,about 2.9 wt % to about 5.2 wt % of the extender, about 53 wt % to about58 wt % of the liquid medium, and about 0.1 wt % to about 9.5 wt % offree urea, mono-methylol urea, di-methylol urea, tri-methylol urea, ureareacted into the aldehyde-based resin, or any combination thereof,wherein all weight percent values are based on the total weight of thebinder, and wherein the sodium hydroxide equivalent weight alkalinity ofthe binder is about 4.5 wt % to about 7.5 wt %.
 7. The binder of claim1, wherein at least a portion of urea in the urea-modifiedphenol-aldehyde resin is covalently bonded with a carbon atom derivedfrom the aldehyde during synthesis of the urea-modified aldehyde-basedresin, and wherein at least a portion of urea in the urea-modifiedphenol-aldehyde resin is: (i) in the form of free urea, (ii) in the formof mono-methylol urea, (iii) in the form of di-methylol urea, (iv) inthe form of tri-methylol urea, or (v) a mixture thereof.
 8. The binderof claim 1, wherein the binder comprises sodium hydroxide, potassiumhydroxide, lithium hydroxide, sodium carbonate, potassium carbonate,calcium carbonate, sodium borate, potassium borate, calcium borate, andzinc borate or a mixture thereof.
 9. The binder of claim 1, wherein thebinder has a viscosity of ≤8,500 cP when maintained at a temperature ofabout 25° C. for at least 8 days after formation of the binder.
 10. Thebinder of claim 1, wherein the binder has a pH of about 11.5 to about12.5.
 11. The binder of claim 1, further comprising about 0.1 wt % toabout 12 wt % of a filler, based on the total weight of the binder. 12.The binder of claim 11, wherein the extender comprises wheat flour, cornflour, or a mixture thereof, and wherein the filler comprises corn cobresidue, a nutshell flour, a fruit pit flour, or a mixture thereof. 13.The binder of claim 1, wherein the sodium hydroxide equivalent weightalkalinity of the binder is about 5.5% to about 7%.
 14. The binder ofclaim 1, further comprising about 0.01 wt % to about 0.5 wt % of asurfactant, based on the total weight of the binder.
 15. The binder ofclaim 1, further comprising about 0.05 wt % to about 3.5 wt % of a salt,based on the total weight of the binder, and wherein the salt comprisessodium chloride, potassium chloride, calcium chloride, sodium sulfate,potassium sulfate, calcium sulfate, magnesium sulfate, or a mixturethereof.
 16. The binder of claim 1, wherein the liquid medium compriseswater.
 17. The binder of claim 1, further comprising about 0.1 wt % toabout 12 wt % of a filler, based on the total weight of the binder,wherein: the urea-modified aldehyde-based resin comprises aurea-modified phenol-formaldehyde resin having a formaldehyde to phenolmolar ratio of about 1.8:1 to about 2.6:1, and at least a portion ofurea in the urea-modified phenol-formaldehyde resin is: covalentlybonded with a carbon atom derived from the aldehyde during synthesis ofthe urea-modified aldehyde-based resin, and at least a portion of theurea in the urea-modified phenol-formaldehyde resin is in the form ofmono-methylol urea, in the form of di-methylol urea, or in the form oftri-methylol urea.
 18. A method for making a composite product,comprising: combining a plurality of lignocellulose substrates and abinder to produce a resinated furnish, wherein the binder comprises:about 30 wt % to about 40 wt % of solids comprising a urea-modifiedaldehyde-based resin; about 0.1 wt % to about 3 wt % of solidscomprising an isocyanate-based resin; about 0.1 wt % to about 12 wt % ofan extender; and about 50 wt % to about 62 wt % of a liquid medium,wherein all weight percent values are based on a total weight of thebinder, and wherein the binder has a sodium hydroxide equivalent weightalkalinity of about 3 wt % to about 9 wt %; and heating the resinatedfurnish to a temperature of about 60° C. to about 300° C. to at leastpartially cure the binder to produce a composite lignocellulose product.19. The method of claim 18, wherein the composite lignocellulose productcomprises structural composite lumber.
 20. A method for making a binder,comprising: contacting solids comprising a urea-modified aldehyde-basedresin, an isocyanate-based resin, an extender, and water to produce thebinder, wherein the binder comprises: about 30 wt % to about 40 wt % ofthe solids comprising the urea-modified aldehyde-based resin; about 0.1wt % to about 3 wt % of solids comprising the isocyanate-based resin;about 0.1 wt % to about 12 wt % of the extender; and about 50 wt % toabout 62 wt % of the liquid medium, wherein all weight percent valuesare based on a total weight of the binder, and wherein the binder has asodium hydroxide equivalent weight alkalinity of about 3 wt % to about 9wt %.